[go: up one dir, main page]

WO2023100025A1 - Flame-retardant laminate - Google Patents

Flame-retardant laminate Download PDF

Info

Publication number
WO2023100025A1
WO2023100025A1 PCT/IB2022/061209 IB2022061209W WO2023100025A1 WO 2023100025 A1 WO2023100025 A1 WO 2023100025A1 IB 2022061209 W IB2022061209 W IB 2022061209W WO 2023100025 A1 WO2023100025 A1 WO 2023100025A1
Authority
WO
WIPO (PCT)
Prior art keywords
binder
laminate
sheet
ammonium polyphosphate
melamine
Prior art date
Application number
PCT/IB2022/061209
Other languages
French (fr)
Inventor
Koen NEL
Kenny MOUTON
Original Assignee
Flooring Industries Limited, Sarl
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 Flooring Industries Limited, Sarl filed Critical Flooring Industries Limited, Sarl
Priority to EP22809530.3A priority Critical patent/EP4440831A1/en
Publication of WO2023100025A1 publication Critical patent/WO2023100025A1/en

Links

Classifications

    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • B44C5/0423—Ornamental plaques, e.g. decorative panels, decorative veneers containing fibreglass elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • B44C5/0461—Ornamental plaques, e.g. decorative panels, decorative veneers used as wall coverings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • B44C5/0469—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper
    • 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
    • B32B2260/028—Paper 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
    • B32B2260/04—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
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B32B2307/738—Thermoformability
    • 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
    • B32B2419/00—Buildings or parts thereof
    • B32B2419/04—Tiles for floors or walls
    • 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
    • B32B2607/00—Walls, panels
    • B32B2607/02—Wall papers, wall coverings
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements

Definitions

  • the present invention relates to laminates, for example such as Direct Pressure Laminates (DPL) and High Pressure Laminates (HPL). Such laminates are used for forming a decorative layer on a substrate, wherein panels with a decorative surface are produced. HPLs are used among other things in the production of furniture, e.g. kitchen furniture. More specifically the invention relates to laminates that possess flameretardant properties.
  • DPL Direct Pressure Laminates
  • HPL High Pressure Laminates
  • High Pressure Laminates are built up from several resin-impregnated sheets, with a decor on top and optionally a protective layer. HPL is produced by pressing the various layers of the HPL together under temperature and pressure, wherein the thermosetting resin is cured. HPL is glued on panels by means of a suitable glue. HPL sheets are for example glued on chipboards, MDF (Medium Density Fiberboard) or HDF (High Density Fiberboard) panels or on Compact Boards (these are panels that comprise sheets of paper impregnated with phenol-formaldehyde resin that have been pressed together). A suitable glue must be selected, depending on the type of panel.
  • DPL Direct Pressure Laminate
  • W02006/111458A1 describes a flame-retardant High Pressure Laminate (HPL).
  • HPL High Pressure Laminate
  • This HPL comprises a first layer of resin-impregnated paper and at least one layer of a fiber- reinforced mat.
  • Each layer of fiber-reinforced mat comprises a binder and a filler.
  • the fillers comprise flame retardants.
  • One aim of the invention is to make improved flame-retardant laminates - High Pressure Laminates and Direct Pressure Laminates - available. It is a specific aim to make flameretardant laminates available that can be produced more easily.
  • the first aspect of the invention relates to a laminate, preferably wherein the laminate is or comprises a High Pressure Laminate (HPL) or a Direct Pressure Laminate (DPL).
  • the laminate comprises a decorative layer, wherein the decorative layer comprises a layer of paper impregnated with an aminoplast resin, preferably wherein the layer of paper is impregnated with melamine-formaldehyde resin.
  • the laminate comprises a sheet, wherein the sheet comprises a non-woven fiberglass that comprises a polymer binder - preferably a thermoplastic binder or a thermosetting binder - and wherein the sheet comprises ammonium polyphosphate (APP).
  • the laminate is characterized in that according to a first option the ammonium polyphosphate is bonded with a second binder on one or on both sides to the non-woven fiberglass bonded with polymer binder, wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; or according to a second option the ammonium polyphosphate is bonded by means of the polymer binder in or to the non-woven fiberglass; and wherein the sheet comprises a second binder on both sides of the sheet; wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea- formaldehyde resin.
  • These laminates according to the invention supply very good fire-retardant properties to panels on which these laminates are applied, either as HPL or as DPL. It is not even necessary that the substrates on which the laminate is applied are flame-retardant. In fact it was found that the presence of the non-woven fiberglass ensures that the panel does not warp in a fire. Warping of panels is, however, observed if the laminate comprises flame-retardant additives but no non-woven fiberglass. If the panel warps, more surface of the panel is exposed to fire, so that considerable heat is released and the board burns through. In the case of panels wherein laminates according to the invention are used, this does not happen and the board does not burn through, but extinguishes the flame.
  • the paper of the decorative layer has an unimpregnated weight between 40 and 120 grams per square meter, for example 120 grams per square meter.
  • the impregnated weight of this paper is preferably between 120 and 300 grams per square meter, more preferably between 150 and 220 grams per square meter, for example 200 grams per square meter.
  • a preferred embodiment is characterized in that the sheet comprises pentaerythritol. It is an advantage of embodiments that the combination of ammonium polyphosphate, melamine and pentaerythritol produces an efficient and effective intumescent fire retardant, so that very good fire-retardant properties are obtained.
  • a preferred embodiment is characterized in that the sheet does not comprise pentaerythritol.
  • ammonium polyphosphate comprises a chain length of more than 100 orthophosphate ions, and preferably comprises more than 500 orthophosphate ions, and more preferably comprises more than 750 orthophosphate ions, and even more preferably comprises more than 1000 orthophosphate ions.
  • This embodiment is especially important for the first option of the first aspect of the invention, in particular the option wherein the ammonium polyphosphate is bonded with a second, thermosetting binder on one or on both sides to the non-woven fiberglass bonded with polymer binder.
  • This embodiment may be obtained by introducing a nonwoven fiberglass impregnated with binder into a bath, wherein this bath comprises at least the second binder and ammonium polyphosphate.
  • this bath comprises at least the second binder and ammonium polyphosphate.
  • the various layers in the laminate are pressed together at elevated temperature. For efficient bonding of the various layers during pressing, sufficient reactivity of the thermosetting binders is necessary; and thus also of the applied second binder of the sheet.
  • thermosetting binders in these layers may react chemically only to a limited extent or not at all during storage, so as not to lose their binding power.
  • Laminates according to the first option and according to these embodiments offer a solution to this, because improved stability of the second, thermosetting binder is obtained, and the impregnated non-woven fiberglass therefore has a longer shelf life. The inventors suspect that this is provided by the long chain length of the ammonium polyphosphates. APPs with long chain length are less soluble in the water-based bath of thermosetting resin - which forms the second binder - together with which they are applied.
  • these APPs are more stable, they release ammonium in the bath less and less quickly. Ammonium would cause a decrease of the pH in the bath of thermosetting resin, so that there is accelerated polymerization of the resin, and thus the stability of the resin is affected adversely.
  • a preferred embodiment is characterized in that the second binder forms a film and in that the film formed by the second binder comprises borax.
  • These embodiments have the advantage that better stability is obtained for the bath with which the second binder is applied.
  • the film formed by the second binder comprises borax' indicates for example that borax is incorporated in the film formed by the second binder. This is for example possible by introducing a non-woven fiberglass impregnated with binder into a bath, wherein the second binder, borax and optionally ammonium polyphosphate are introduced into this bath or wherein at least the second binder, wherein this second binder comprises borax, and optionally ammonium polyphosphate, are introduced into this bath.
  • a preferred embodiment is characterized in that the non-woven fiberglass is a wet laid non-woven fiberglass.
  • a preferred embodiment is characterized in that the polymer binder is or comprises a polyvinyl alcohol.
  • a preferred embodiment is characterized in that the decorative layer comprises a dyed or printed layer of paper.
  • a preferred embodiment is characterized in that the laminate comprises one or more layers of paper impregnated with a resin, wherein the non-woven fiberglass is located between the decorative layer and the one or more layers of paper.
  • the one or more layers of paper are layers of kraft paper, preferably impregnated with a phenol-formaldehyde resin, more preferably impregnated with a phenol-formaldehyde resin that comprises melamine formaldehyde.
  • phenol-formaldehyde resins that comprise melamine has the advantage that the resin has a higher reactivity.
  • this kraft paper has a weight - before impregnation - between 80 and 200 grams per square meter, for example 120 grams per square meter.
  • the one or more impregnated layers of paper do not comprise ammonium polyphosphate.
  • This embodiment gives good fire resistance; and allows standard impregnated paper - for example standard impregnated kraft paper - to be used.
  • the laminate does not comprise any layers that comprise ammonium polyphosphate situated on the other side of the non-woven fiberglass than the side with the decorative layer.
  • ammonium polyphosphate situated on the other side of the non-woven fiberglass than the side with the decorative layer.
  • a preferred embodiment is characterized in that a transparent or translucent wear layer is applied on the decorative layer, for example by means of a layer of paper impregnated with resin - preferably with melamine-formaldehyde resin - or by means of a resin coating, for example an acrylate or polyurethane acrylate coating layer.
  • this wear layer comprises particles in order to increase the abrasion resistance of the wear layer.
  • the weight of glass in the non-woven fiberglass is between 50 and 200 grams per square meter, more preferably between 50 and 120 grams per square meter, for example 80 grams per square meter.
  • a preferred embodiment is characterized in that the aminoplast resin is a melamineformaldehyde resin or a melamine-urea-formaldehyde resin. These embodiments ensure even better fire-retardant properties. The inventors suspect that the melamine present gives rise to an increased intumescent effect.
  • a preferred embodiment is characterized in that the laminate comprises between 40 and 200 grams of ammonium polyphosphate per square meter, more preferably between 40 and 180 grams of ammonium polyphosphate per square meter; and more preferably between 100 and 150 grams of ammonium polyphosphate per square meter. These amounts were found to give optimal properties relating to fire resistance, while maintaining the other properties of the laminate.
  • a preferred embodiment is characterized in that the ammonium polyphosphate is bonded with a second binder on one or on both sides to the binder-impregnated non-woven fiberglass, wherein this second binder is a thermosetting binder - preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin - wherein the second binder forms a film and in that borax and/or triethylamine or reaction products of triethylamine are incorporated in the film formed by the second binder.
  • These embodiments have the advantage that fire-retardant properties that are more constant and more controllable are obtained. The inventors suspect that this is due to the addition of borax and/or tri ethylamine to the bath with which the second binder is applied, so that the bath is stabilized. As a result, the second binder can be applied more stably.
  • a preferred embodiment is characterized in that the laminate is an HPL (High Pressure Laminate), wherein the decorative layer, the non-woven fiberglass and optionally other impregnated layers have been pressed together at elevated temperature and pressure.
  • HPL High Pressure Laminate
  • This embodiment allows fire-resistant HPL laminates to be made, which are usable as a decorative layer in order to produce fire-retardant panels.
  • a preferred embodiment is characterized in that the laminate is a Continuous Pressure Laminate (CPL).
  • CPL Continuous Pressure Laminate
  • the second aspect of the invention relates to a panel, characterized in that the panel comprises a substrate and a laminate such as in any embodiment of the first aspect of the invention.
  • An advantage of panels according to the second aspect of the invention is that fire-resistant panels are obtained.
  • the substrate is or comprises a plurality of layers of paper bonded to each other by means of phenol-formaldehyde resin, a chipboard, an MDF board or an HDF board.
  • the wood fibers are glued together by means of a urea-formaldehyde resin or by means of a pMDI (polymeric methylene diphenyl diisocyanate).
  • a urea-formaldehyde resin or by means of a pMDI (polymeric methylene diphenyl diisocyanate).
  • One embodiment of the second aspect of the invention is characterized in that the substrate does not comprise any ammonium polyphosphate.
  • the inventors discovered that even without ammonium polyphosphate in the substrate, the panel has good fire- retardant properties.
  • One embodiment of the second aspect of the invention is characterized in that the laminate is a High Pressure Laminate and is bonded to the substrate with a layer of glue.
  • One embodiment of the second aspect of the invention is characterized in that the laminate is a Direct Pressure Laminate.
  • the third aspect of the invention relates to a sheet, wherein the sheet comprises a nonwoven fiberglass that comprises a polymer binder - preferably a thermoplastic binder or a thermosetting binder - and wherein the sheet comprises ammonium polyphosphate (APP).
  • APP ammonium polyphosphate
  • the sheet is characterized in that according to a first option, the ammonium polyphosphate is bonded with a second binder on one or on both sides to the non-woven fiberglass bonded with polymer binder, wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; or according to a second option the ammonium polyphosphate is bonded by means of the polymer binder in or to the non-woven fiberglass; and wherein the sheet comprises a second binder on both sides of the sheet; wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; and wherein both according to the first option and according to the second option the second binder is in B-stage.
  • this second binder is a thermosetting binder, preferably wherein the
  • the sheet according to the third aspect of the invention has good flame-retardant properties.
  • the sheet may be laminated by means of pressure and elevated temperature on a substrate, wherein the second binder will cure and will provide binding with the substrate.
  • One embodiment of the third aspect of the invention is characterized in that the sheet has a weight between 250-400 grams per square meter, more preferably between 300-350 grams per square meter.
  • One embodiment of the third aspect of the invention is characterized in that the sheet comprises pentaerythritol.
  • An advantage of these embodiments is that the combination of ammonium polyphosphate, melamine and pentaerythritol produces an efficient and effective intumescent fire retardant.
  • One embodiment of the third aspect of the invention is characterized in that the sheet does not comprise pentaerythritol. Good fire-retardant results were also obtained without pentaerythritol.
  • ammonium polyphosphate comprises a chain length of more than 100 orthophosphate ions, and more preferably comprises more than 500 orthophosphate ions, and more preferably comprises more than 750 orthophosphate ions, and even more preferably comprises more than 1000 orthophosphate ions.
  • This embodiment is especially important for the first option; this is the option wherein the ammonium polyphosphate is bonded with a second, thermosetting binder on one or on both sides to the non-woven fiberglass bonded with polymer binder.
  • thermosetting binders in these layers may react chemically only to a limited extent or not at all, so as not to lose their binding power.
  • Laminates according to the second option and according to these embodiments offer a solution to this, because improved stability of the second, thermosetting binder is obtained, and the impregnated non-woven fiberglass has a longer shelf life.
  • APPs with a long chain length are less soluble in the water-based bath of thermosetting resin - which forms the second binder - together with which they are applied. As a result, these APPs are more stable, they release ammonium in the bath less and less quickly. Ammonium would cause a decrease of the pH in the bath of thermosetting resin, so that there is accelerated polymerization of the resin, and thus the stability of the resin is affected adversely.
  • One embodiment of the third aspect of the invention is characterized in that the second binder forms a film and the film formed by the second binder comprises borax.
  • Borax may be incorporated in the film because the bath with which the second binder is applied comprises borax.
  • the film formed by the second binder comprises borax' indicates for example that borax is incorporated in the film formed by the second binder.
  • the presence of borax ensures more stable fire-retardant properties of the sheet. The inventors suspect that this is due to the buffering action of borax in the bath with which the second binder is applied, so that this bath has better stability.
  • One embodiment of the third aspect of the invention is characterized in that the nonwoven fiberglass is a wet laid non-woven fiberglass.
  • One embodiment of the third aspect of the invention is characterized in that the polymer binder is or comprises a polyvinyl alcohol.
  • One embodiment of the third aspect of the invention is characterized in that the weight of glass in the non-woven fiberglass is between 50 and 200 grams per square meter, more preferably between 50 and 120 grams per square meter, e.g. 80 grams per square meter. These embodiments were found to give optimal properties.
  • One embodiment of the third aspect of the invention is characterized in that the sheet comprises between 40 and 200 grams of ammonium polyphosphate per square meter, more preferably between 40 and 180 grams of ammonium polyphosphate per square meter; and more preferably between 100 and 150 grams of ammonium polyphosphate per square meter. These amounts were found to give optimal properties relating to fire resistance, while maintaining the other properties of the laminate.
  • One embodiment of the third aspect of the invention is characterized in that the ammonium polyphosphate is bonded with a second binder on both sides to the binder- impregnated non-woven fiberglass, wherein this second binder is a thermosetting binder - preferably wherein the second binder is a melamine-formaldehyde resin or a melamine- urea-formaldehyde resin - wherein the second binder forms a film and wherein borax and/or triethylamine or reaction products of triethylamine are incorporated in the film formed by the second binder.
  • These embodiments have the advantage that fire-retardant properties that are more constant and more controllable are obtained. The inventors suspect that this is due to the addition of borax and/or triethylamine to the bath with which the second binder is applied, so that the bath is stabilized. As a result, the second binder can be applied more stably.
  • the fourth aspect of the invention relates to a method of producing a sheet, optionally a sheet such as in any embodiment of the third aspect of the invention.
  • the method comprises the step of impregnating a non-woven fiberglass in a bath; wherein the bath comprises a thermosetting binder, preferably wherein the thermosetting binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; and wherein the bath comprises ammonium polyphosphate (APP) or wherein ammonium polyphosphate (APP) is spread on the wet non-woven fiberglass impregnated with thermosetting binder; and wherein the method comprises the step of drying to B-stage after impregnation in the bath.
  • the bath comprises a thermosetting binder, preferably wherein the thermosetting binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin
  • the bath comprises ammonium polyphosphate (APP) or wherein ammoni
  • This method allows sheets to be made efficiently, which have flame-retardant properties and which can be laminated on a substrate by means of pressure and elevated temperature.
  • the nonwoven fiberglass comprises a polymer binder - preferably a thermoplastic binder or a thermosetting binder.
  • One embodiment of the fourth aspect of the invention is characterized in that the polymer binder is or comprises a polyvinyl alcohol.
  • One embodiment of the fourth aspect of the invention is characterized in that in the method, a sheet is produced with a weight between 250-400 grams per square meter, more preferably between 300-350 grams per square meter.
  • One embodiment of the fourth aspect of the invention is characterized in that the nonwoven fiberglass is a wet laid non-woven fiberglass.
  • One embodiment of the fourth aspect of the invention is characterized in that the weight of glass in the non-woven fiberglass is between 50 and 200 grams per square meter, more preferably between 50 and 120 grams per square meter, e.g. 80 grams per square meter.
  • One embodiment of the fourth aspect of the invention is characterized in that the bath comprises pentaerythritol.
  • An advantage of these embodiments is that the combination of ammonium polyphosphate, melamine and pentaerythritol produces an efficient and effective intumescent fire retardant.
  • One embodiment of the fourth aspect of the invention is characterized in that the bath does not comprise pentaerythritol. Good results were also obtained without pentaerythritol.
  • ammonium polyphosphate comprises a chain length of more than 100 orthophosphate ions, and more preferably comprises more than 500 orthophosphate ions, and more preferably comprises more than 750 orthophosphate ions, and even more preferably comprises more than 1000 orthophosphate ions.
  • thermosetting binders in the various layers that will form the laminate - have a sufficient shelflife. This means that the thermosetting binders in these layers may react chemically only to a limited extent or not at all during storage, so as not to lose their binding power.
  • Sheets produced according to this embodiment of the method of the fourth aspect of the invention offer a solution to this, because improved stability of the thermosetting binder in the sheet is obtained, and the impregnated non-woven fiberglass therefore has a longer shelf life.
  • APPs with a long chain length are less soluble in the water-based bath of thermosetting resin together with which they are applied. As a result, these APPs are more stable, they release ammonium in the bath less and less quickly. Ammonium would cause a decrease of the pH in the bath of thermosetting resin, so that there is accelerated polymerization of the resin, and thus the stability of the resin is affected adversely.
  • the bath comprises a buffer, for example borax or triethylamine or reaction products of triethylamine.
  • a buffer for example borax or triethylamine or reaction products of triethylamine.
  • One embodiment of the fourth aspect of the invention is characterized in that in the method, the non-woven fiberglass is impregnated so that the sheet produced comprises between 40 and 200 grams of ammonium polyphosphate per square meter, more preferably between 40 and 180 grams of ammonium polyphosphate per square meter; and more preferably between 100 and 150 grams of ammonium polyphosphate per square meter.
  • Fig. 1 presents a laminate according to the invention
  • Fig. 2 illustrates an example of a panel according to the invention.
  • Fig. 1 presents a laminate 1 according to the invention.
  • the laminate comprises a decorative layer 12.
  • the decorative layer consists of a printed layer of paper impregnated with melamine-formaldehyde resin.
  • the laminate comprises a sheet 10.
  • the sheet comprises a non-woven fiberglass that comprises a polymer binder; the sheet also comprises ammonium polyphosphate (APP).
  • APP ammonium polyphosphate
  • the non-woven fiberglass is a wet laid non-woven fiberglass.
  • the ammonium polyphosphate may, according to a first option, be bonded with a second binder on one or on both sides to the non-woven fiberglass bonded with polymer binder, wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin.
  • the ammonium polyphosphate may, according to a second option, be bonded by means of the polymer binder in or on the non-woven fiberglass; wherein the sheet comprises a second binder on both sides of the sheet; wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin.
  • the film formed by the second binder comprises borax.
  • the sheet comprises pentaerythritol.
  • the ammonium polyphosphate has a chain length of more than 1000 orthophosphate ions.
  • a specific example of a sheet according to the invention comprises a nonwoven nonwoven fiberglass that has been produced by a wet process, according to the so-called wet laid process.
  • This non-woven fiberglass comprises 160 grams per square meter of glass fibers of discrete length, which are bonded together by means of 20 grams per square meter of polyvinyl alcohol.
  • This nonwoven non-woven fiberglass was impregnated with melamine-formaldehyde resin to a weight of 420 grams per square meter.
  • the melamine-formaldehyde resin comprises in dispersion ammonium polyphosphate (APP) with a chain length equal to or greater than 1000, so that the non-woven fiberglass impregnated with melamineformaldehyde comprises 48 grams per square meter of this ammonium polyphosphate.
  • the melamine-formaldehyde resin further comprised borax as buffer. Triethylamine may also be used as buffer instead of borax.
  • This impregnated non-woven fiberglass was dried to 5 to 8 percent residual moisture content, so that the melamine-formaldehyde resin is in B-stage.
  • the melamine-formaldehyde resin may comprise pentaerythritol, but this is not necessary for the invention.
  • a second example of a sheet according to the invention comprises a nonwoven nonwoven fiberglass that has been produced by a wet process, according to the so-called wet laid process.
  • This non-woven fiberglass comprises 57 grams per square meter of glass fibers of discrete length, which are bonded together by means of 10 grams per square meter of polyvinyl alcohol.
  • This nonwoven non-woven fiberglass was impregnated in two steps with melamine- formaldehyde resin to a weight of 400 grams per square meter.
  • the melamine- formaldehyde resin comprises in dispersion ammonium polyphosphate (APP) with a chain length greater than or equal to 1000, so that the non-woven fiberglass impregnated with melamine-formaldehyde comprises 166 grams per square meter of this ammonium polyphosphate.
  • the melamine-formaldehyde resin further comprised borax as a buffer. Triethylamine may also be used as a buffer instead of borax.
  • the melamine-formaldehyde resin was in B-stage.
  • the melamine-formaldehyde resin may comprise pentaerythritol, but this is not necessary for the invention.
  • the laminate 1 further comprises a number of - for example three - layers of paper 16 impregnated with a resin.
  • the sheet 10 is located between the decorative layer 12 and the one or more layers of paper 16.
  • the layers of paper 16 may be layers of kraft paper, impregnated with phenol-formaldehyde resin.
  • the laminate 1 in Fig. 1 comprises a transparent or translucent wear layer 14, applied on the decorative layer.
  • the wear layer 14 comprises a layer of paper impregnated by means of a melamine-formaldehyde resin.
  • this wear layer comprises particles in order to increase the abrasion resistance of the wear layer.
  • the laminate may be produced by laying the various layers on one another and crosslinking the resins by means of pressure and elevated temperature.
  • Fig. 2 illustrates an example of a panel according to the invention.
  • the panel comprises a substrate 18 and a laminate 1 such as in the first aspect of the invention, for example a laminate such as in Fig. 1.
  • the reference numbers in Fig. 2 thus have the same meaning as the corresponding reference numbers in Fig. 1.
  • the substrate 18 may for example be or comprise a plurality of layers of paper bonded to each other by means of phenol-formaldehyde resin, a chipboard, an MDF board or an HDF board, preferably without this substrate comprising ammonium polyphosphate.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

The laminate comprises a decorative layer and a sheet. The sheet comprises a non-woven fiberglass that comprises a polymer binder. The sheet comprises ammonium polyphosphate that is bonded by means of the polymer binder in or on the non-woven fiberglass, or that is bonded with a thermosetting binder on both sides to the non-woven fiberglass bonded with polymer binder.

Description

Flame-retardant laminate
The present invention relates to laminates, for example such as Direct Pressure Laminates (DPL) and High Pressure Laminates (HPL). Such laminates are used for forming a decorative layer on a substrate, wherein panels with a decorative surface are produced. HPLs are used among other things in the production of furniture, e.g. kitchen furniture. More specifically the invention relates to laminates that possess flameretardant properties.
High Pressure Laminates (HPL) are built up from several resin-impregnated sheets, with a decor on top and optionally a protective layer. HPL is produced by pressing the various layers of the HPL together under temperature and pressure, wherein the thermosetting resin is cured. HPL is glued on panels by means of a suitable glue. HPL sheets are for example glued on chipboards, MDF (Medium Density Fiberboard) or HDF (High Density Fiberboard) panels or on Compact Boards (these are panels that comprise sheets of paper impregnated with phenol-formaldehyde resin that have been pressed together). A suitable glue must be selected, depending on the type of panel.
In the case of Direct Pressure Laminate (DPL), layers similar to layers used in the production of HPL are pressed directly under temperature and pressure on a substrate. The mutual bonding of the various layers occurs at the same moment as binding on the substrate, by means of the thermosetting resin that the layer or layers of the DPL comprise.
W02006/111458A1 describes a flame-retardant High Pressure Laminate (HPL). This HPL comprises a first layer of resin-impregnated paper and at least one layer of a fiber- reinforced mat. Each layer of fiber-reinforced mat comprises a binder and a filler. The fillers comprise flame retardants. One aim of the invention is to make improved flame-retardant laminates - High Pressure Laminates and Direct Pressure Laminates - available. It is a specific aim to make flameretardant laminates available that can be produced more easily.
The first aspect of the invention relates to a laminate, preferably wherein the laminate is or comprises a High Pressure Laminate (HPL) or a Direct Pressure Laminate (DPL). The laminate comprises a decorative layer, wherein the decorative layer comprises a layer of paper impregnated with an aminoplast resin, preferably wherein the layer of paper is impregnated with melamine-formaldehyde resin. The laminate comprises a sheet, wherein the sheet comprises a non-woven fiberglass that comprises a polymer binder - preferably a thermoplastic binder or a thermosetting binder - and wherein the sheet comprises ammonium polyphosphate (APP). The laminate is characterized in that according to a first option the ammonium polyphosphate is bonded with a second binder on one or on both sides to the non-woven fiberglass bonded with polymer binder, wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; or according to a second option the ammonium polyphosphate is bonded by means of the polymer binder in or to the non-woven fiberglass; and wherein the sheet comprises a second binder on both sides of the sheet; wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea- formaldehyde resin.
These laminates according to the invention supply very good fire-retardant properties to panels on which these laminates are applied, either as HPL or as DPL. It is not even necessary that the substrates on which the laminate is applied are flame-retardant. In fact it was found that the presence of the non-woven fiberglass ensures that the panel does not warp in a fire. Warping of panels is, however, observed if the laminate comprises flame-retardant additives but no non-woven fiberglass. If the panel warps, more surface of the panel is exposed to fire, so that considerable heat is released and the board burns through. In the case of panels wherein laminates according to the invention are used, this does not happen and the board does not burn through, but extinguishes the flame. Preferably the paper of the decorative layer has an unimpregnated weight between 40 and 120 grams per square meter, for example 120 grams per square meter. The impregnated weight of this paper is preferably between 120 and 300 grams per square meter, more preferably between 150 and 220 grams per square meter, for example 200 grams per square meter.
A preferred embodiment is characterized in that the sheet comprises pentaerythritol. It is an advantage of embodiments that the combination of ammonium polyphosphate, melamine and pentaerythritol produces an efficient and effective intumescent fire retardant, so that very good fire-retardant properties are obtained.
A preferred embodiment is characterized in that the sheet does not comprise pentaerythritol.
Good fire-retardant results have been obtained without pentaerythritol.
A preferred embodiment is characterized in that the ammonium polyphosphate comprises a chain length of more than 100 orthophosphate ions, and preferably comprises more than 500 orthophosphate ions, and more preferably comprises more than 750 orthophosphate ions, and even more preferably comprises more than 1000 orthophosphate ions.
This embodiment is especially important for the first option of the first aspect of the invention, in particular the option wherein the ammonium polyphosphate is bonded with a second, thermosetting binder on one or on both sides to the non-woven fiberglass bonded with polymer binder. This embodiment may be obtained by introducing a nonwoven fiberglass impregnated with binder into a bath, wherein this bath comprises at least the second binder and ammonium polyphosphate. During production of the laminates - either HPL or DPL - the various layers in the laminate are pressed together at elevated temperature. For efficient bonding of the various layers during pressing, sufficient reactivity of the thermosetting binders is necessary; and thus also of the applied second binder of the sheet. It is desirable that for the pressing operation these various layers - and particularly the thermosetting binders in these layers - have a sufficient shelf life. This means that the thermosetting binders in these layers may react chemically only to a limited extent or not at all during storage, so as not to lose their binding power. Laminates according to the first option and according to these embodiments offer a solution to this, because improved stability of the second, thermosetting binder is obtained, and the impregnated non-woven fiberglass therefore has a longer shelf life. The inventors suspect that this is provided by the long chain length of the ammonium polyphosphates. APPs with long chain length are less soluble in the water-based bath of thermosetting resin - which forms the second binder - together with which they are applied. As a result, these APPs are more stable, they release ammonium in the bath less and less quickly. Ammonium would cause a decrease of the pH in the bath of thermosetting resin, so that there is accelerated polymerization of the resin, and thus the stability of the resin is affected adversely.
A preferred embodiment is characterized in that the second binder forms a film and in that the film formed by the second binder comprises borax. These embodiments have the advantage that better stability is obtained for the bath with which the second binder is applied. 'The film formed by the second binder comprises borax' indicates for example that borax is incorporated in the film formed by the second binder. This is for example possible by introducing a non-woven fiberglass impregnated with binder into a bath, wherein the second binder, borax and optionally ammonium polyphosphate are introduced into this bath or wherein at least the second binder, wherein this second binder comprises borax, and optionally ammonium polyphosphate, are introduced into this bath.
A preferred embodiment is characterized in that the non-woven fiberglass is a wet laid non-woven fiberglass.
A preferred embodiment is characterized in that the polymer binder is or comprises a polyvinyl alcohol.
A preferred embodiment is characterized in that the decorative layer comprises a dyed or printed layer of paper. A preferred embodiment is characterized in that the laminate comprises one or more layers of paper impregnated with a resin, wherein the non-woven fiberglass is located between the decorative layer and the one or more layers of paper.
More preferably, the one or more layers of paper are layers of kraft paper, preferably impregnated with a phenol-formaldehyde resin, more preferably impregnated with a phenol-formaldehyde resin that comprises melamine formaldehyde.
The use of phenol-formaldehyde resins that comprise melamine has the advantage that the resin has a higher reactivity.
Preferably this kraft paper has a weight - before impregnation - between 80 and 200 grams per square meter, for example 120 grams per square meter.
Preferably the one or more impregnated layers of paper do not comprise ammonium polyphosphate. This embodiment gives good fire resistance; and allows standard impregnated paper - for example standard impregnated kraft paper - to be used.
Preferably the laminate does not comprise any layers that comprise ammonium polyphosphate situated on the other side of the non-woven fiberglass than the side with the decorative layer. These embodiments allow the structure of the laminate to be kept simple, while good fire resistance is still obtained.
A preferred embodiment is characterized in that a transparent or translucent wear layer is applied on the decorative layer, for example by means of a layer of paper impregnated with resin - preferably with melamine-formaldehyde resin - or by means of a resin coating, for example an acrylate or polyurethane acrylate coating layer. Optionally this wear layer comprises particles in order to increase the abrasion resistance of the wear layer. A preferred embodiment is characterized in that the weight of glass in the non-woven fiberglass is between 50 and 200 grams per square meter, more preferably between 50 and 120 grams per square meter, for example 80 grams per square meter.
A preferred embodiment is characterized in that the aminoplast resin is a melamineformaldehyde resin or a melamine-urea-formaldehyde resin. These embodiments ensure even better fire-retardant properties. The inventors suspect that the melamine present gives rise to an increased intumescent effect.
A preferred embodiment is characterized in that the laminate comprises between 40 and 200 grams of ammonium polyphosphate per square meter, more preferably between 40 and 180 grams of ammonium polyphosphate per square meter; and more preferably between 100 and 150 grams of ammonium polyphosphate per square meter. These amounts were found to give optimal properties relating to fire resistance, while maintaining the other properties of the laminate.
A preferred embodiment is characterized in that the ammonium polyphosphate is bonded with a second binder on one or on both sides to the binder-impregnated non-woven fiberglass, wherein this second binder is a thermosetting binder - preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin - wherein the second binder forms a film and in that borax and/or triethylamine or reaction products of triethylamine are incorporated in the film formed by the second binder. These embodiments have the advantage that fire-retardant properties that are more constant and more controllable are obtained. The inventors suspect that this is due to the addition of borax and/or tri ethylamine to the bath with which the second binder is applied, so that the bath is stabilized. As a result, the second binder can be applied more stably.
A preferred embodiment is characterized in that the laminate is an HPL (High Pressure Laminate), wherein the decorative layer, the non-woven fiberglass and optionally other impregnated layers have been pressed together at elevated temperature and pressure. This embodiment allows fire-resistant HPL laminates to be made, which are usable as a decorative layer in order to produce fire-retardant panels.
A preferred embodiment is characterized in that the laminate is a Continuous Pressure Laminate (CPL).
The second aspect of the invention relates to a panel, characterized in that the panel comprises a substrate and a laminate such as in any embodiment of the first aspect of the invention. An advantage of panels according to the second aspect of the invention is that fire-resistant panels are obtained.
One embodiment of the second aspect of the invention is characterized in that the substrate is or comprises a plurality of layers of paper bonded to each other by means of phenol-formaldehyde resin, a chipboard, an MDF board or an HDF board.
Preferably in the MDF board or the HDF board the wood fibers are glued together by means of a urea-formaldehyde resin or by means of a pMDI (polymeric methylene diphenyl diisocyanate).
One embodiment of the second aspect of the invention is characterized in that the substrate does not comprise any ammonium polyphosphate. The inventors discovered that even without ammonium polyphosphate in the substrate, the panel has good fire- retardant properties.
One embodiment of the second aspect of the invention is characterized in that the laminate is a High Pressure Laminate and is bonded to the substrate with a layer of glue.
One embodiment of the second aspect of the invention is characterized in that the laminate is a Direct Pressure Laminate.
One embodiment of the second aspect of the invention is characterized in that the panel is a wall panel, a ceiling panel or a furniture panel. The third aspect of the invention relates to a sheet, wherein the sheet comprises a nonwoven fiberglass that comprises a polymer binder - preferably a thermoplastic binder or a thermosetting binder - and wherein the sheet comprises ammonium polyphosphate (APP). The sheet is characterized in that according to a first option, the ammonium polyphosphate is bonded with a second binder on one or on both sides to the non-woven fiberglass bonded with polymer binder, wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; or according to a second option the ammonium polyphosphate is bonded by means of the polymer binder in or to the non-woven fiberglass; and wherein the sheet comprises a second binder on both sides of the sheet; wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; and wherein both according to the first option and according to the second option the second binder is in B-stage.
The sheet according to the third aspect of the invention has good flame-retardant properties. The sheet may be laminated by means of pressure and elevated temperature on a substrate, wherein the second binder will cure and will provide binding with the substrate.
One embodiment of the third aspect of the invention is characterized in that the sheet has a weight between 250-400 grams per square meter, more preferably between 300-350 grams per square meter.
One embodiment of the third aspect of the invention is characterized in that the sheet comprises pentaerythritol.
An advantage of these embodiments is that the combination of ammonium polyphosphate, melamine and pentaerythritol produces an efficient and effective intumescent fire retardant. One embodiment of the third aspect of the invention is characterized in that the sheet does not comprise pentaerythritol. Good fire-retardant results were also obtained without pentaerythritol.
One embodiment of the third aspect of the invention is characterized in that the ammonium polyphosphate comprises a chain length of more than 100 orthophosphate ions, and more preferably comprises more than 500 orthophosphate ions, and more preferably comprises more than 750 orthophosphate ions, and even more preferably comprises more than 1000 orthophosphate ions.
This embodiment is especially important for the first option; this is the option wherein the ammonium polyphosphate is bonded with a second, thermosetting binder on one or on both sides to the non-woven fiberglass bonded with polymer binder.
During production of the laminates - whether HPL (High Pressure Laminate) or DPL (Direct Pressure Laminate) - the various layers in the laminate are pressed together at elevated temperature. For efficient bonding of the various layers during pressing, sufficient reactivity of the thermosetting binders is necessary; and thus also of the applied second binder of the sheet. It is desirable that for the pressing operation these various layers - and particularly the thermosetting binders in these layers - have a sufficient shelf life. This means that the thermosetting binders in these layers may react chemically only to a limited extent or not at all, so as not to lose their binding power. Laminates according to the second option and according to these embodiments offer a solution to this, because improved stability of the second, thermosetting binder is obtained, and the impregnated non-woven fiberglass has a longer shelf life. The inventors suspect that this is due to the long chain length of the ammonium polyphosphates. APPs with a long chain length are less soluble in the water-based bath of thermosetting resin - which forms the second binder - together with which they are applied. As a result, these APPs are more stable, they release ammonium in the bath less and less quickly. Ammonium would cause a decrease of the pH in the bath of thermosetting resin, so that there is accelerated polymerization of the resin, and thus the stability of the resin is affected adversely. One embodiment of the third aspect of the invention is characterized in that the second binder forms a film and the film formed by the second binder comprises borax. Borax may be incorporated in the film because the bath with which the second binder is applied comprises borax. 'The film formed by the second binder comprises borax' indicates for example that borax is incorporated in the film formed by the second binder. The presence of borax ensures more stable fire-retardant properties of the sheet. The inventors suspect that this is due to the buffering action of borax in the bath with which the second binder is applied, so that this bath has better stability.
One embodiment of the third aspect of the invention is characterized in that the nonwoven fiberglass is a wet laid non-woven fiberglass.
One embodiment of the third aspect of the invention is characterized in that the polymer binder is or comprises a polyvinyl alcohol.
One embodiment of the third aspect of the invention is characterized in that the weight of glass in the non-woven fiberglass is between 50 and 200 grams per square meter, more preferably between 50 and 120 grams per square meter, e.g. 80 grams per square meter. These embodiments were found to give optimal properties.
One embodiment of the third aspect of the invention is characterized in that the sheet comprises between 40 and 200 grams of ammonium polyphosphate per square meter, more preferably between 40 and 180 grams of ammonium polyphosphate per square meter; and more preferably between 100 and 150 grams of ammonium polyphosphate per square meter. These amounts were found to give optimal properties relating to fire resistance, while maintaining the other properties of the laminate.
One embodiment of the third aspect of the invention is characterized in that the ammonium polyphosphate is bonded with a second binder on both sides to the binder- impregnated non-woven fiberglass, wherein this second binder is a thermosetting binder - preferably wherein the second binder is a melamine-formaldehyde resin or a melamine- urea-formaldehyde resin - wherein the second binder forms a film and wherein borax and/or triethylamine or reaction products of triethylamine are incorporated in the film formed by the second binder. These embodiments have the advantage that fire-retardant properties that are more constant and more controllable are obtained. The inventors suspect that this is due to the addition of borax and/or triethylamine to the bath with which the second binder is applied, so that the bath is stabilized. As a result, the second binder can be applied more stably.
The fourth aspect of the invention relates to a method of producing a sheet, optionally a sheet such as in any embodiment of the third aspect of the invention. The method comprises the step of impregnating a non-woven fiberglass in a bath; wherein the bath comprises a thermosetting binder, preferably wherein the thermosetting binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; and wherein the bath comprises ammonium polyphosphate (APP) or wherein ammonium polyphosphate (APP) is spread on the wet non-woven fiberglass impregnated with thermosetting binder; and wherein the method comprises the step of drying to B-stage after impregnation in the bath.
This method allows sheets to be made efficiently, which have flame-retardant properties and which can be laminated on a substrate by means of pressure and elevated temperature.
One embodiment of the fourth aspect of the invention is characterized in that the nonwoven fiberglass comprises a polymer binder - preferably a thermoplastic binder or a thermosetting binder.
One embodiment of the fourth aspect of the invention is characterized in that the polymer binder is or comprises a polyvinyl alcohol.
One embodiment of the fourth aspect of the invention is characterized in that in the method, a sheet is produced with a weight between 250-400 grams per square meter, more preferably between 300-350 grams per square meter. One embodiment of the fourth aspect of the invention is characterized in that the nonwoven fiberglass is a wet laid non-woven fiberglass.
One embodiment of the fourth aspect of the invention is characterized in that the weight of glass in the non-woven fiberglass is between 50 and 200 grams per square meter, more preferably between 50 and 120 grams per square meter, e.g. 80 grams per square meter.
One embodiment of the fourth aspect of the invention is characterized in that the bath comprises pentaerythritol.
An advantage of these embodiments is that the combination of ammonium polyphosphate, melamine and pentaerythritol produces an efficient and effective intumescent fire retardant.
One embodiment of the fourth aspect of the invention is characterized in that the bath does not comprise pentaerythritol. Good results were also obtained without pentaerythritol.
One embodiment of the fourth aspect of the invention is characterized in that the ammonium polyphosphate comprises a chain length of more than 100 orthophosphate ions, and more preferably comprises more than 500 orthophosphate ions, and more preferably comprises more than 750 orthophosphate ions, and even more preferably comprises more than 1000 orthophosphate ions.
During production of laminates - whether HPL or DPL - making use of the sheet produced by the method of the fourth aspect of the invention, the various layers in the laminate are pressed together at elevated temperature. For efficient bonding of the various layers during pressing, sufficient reactivity of the thermosetting binders is necessary; and thus also of the applied thermosetting binder of the sheet. It is desirable that for the pressing operation these various layers - and particularly the thermosetting binders in the various layers that will form the laminate - have a sufficient shelflife. This means that the thermosetting binders in these layers may react chemically only to a limited extent or not at all during storage, so as not to lose their binding power. Sheets produced according to this embodiment of the method of the fourth aspect of the invention offer a solution to this, because improved stability of the thermosetting binder in the sheet is obtained, and the impregnated non-woven fiberglass therefore has a longer shelf life. The inventors suspect that this is due to the long chain length of the ammonium polyphosphates. APPs with a long chain length are less soluble in the water-based bath of thermosetting resin together with which they are applied. As a result, these APPs are more stable, they release ammonium in the bath less and less quickly. Ammonium would cause a decrease of the pH in the bath of thermosetting resin, so that there is accelerated polymerization of the resin, and thus the stability of the resin is affected adversely.
One embodiment of the fourth aspect of the invention is characterized in that the bath comprises a buffer, for example borax or triethylamine or reaction products of triethylamine. These embodiments have the advantage that fire-retardant properties that are more constant and more controllable are obtained in the sheet that is produced in the method. The inventors suspect that this is due to the buffer, so that the bath is stabilized. As a result, the melamine resin can be applied more stably.
One embodiment of the fourth aspect of the invention is characterized in that in the method, the non-woven fiberglass is impregnated so that the sheet produced comprises between 40 and 200 grams of ammonium polyphosphate per square meter, more preferably between 40 and 180 grams of ammonium polyphosphate per square meter; and more preferably between 100 and 150 grams of ammonium polyphosphate per square meter.
For better illustration of the features of the invention, some preferred embodiments are described hereunder, as examples without any limiting character, referring to the appended drawings, in which:
Fig. 1 presents a laminate according to the invention;
Fig. 2 illustrates an example of a panel according to the invention. Fig. 1 presents a laminate 1 according to the invention. The laminate comprises a decorative layer 12. In the example, the decorative layer consists of a printed layer of paper impregnated with melamine-formaldehyde resin. The laminate comprises a sheet 10. The sheet comprises a non-woven fiberglass that comprises a polymer binder; the sheet also comprises ammonium polyphosphate (APP). In the example the non-woven fiberglass is a wet laid non-woven fiberglass.
The ammonium polyphosphate may, according to a first option, be bonded with a second binder on one or on both sides to the non-woven fiberglass bonded with polymer binder, wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin.
The ammonium polyphosphate may, according to a second option, be bonded by means of the polymer binder in or on the non-woven fiberglass; wherein the sheet comprises a second binder on both sides of the sheet; wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin. Preferably the film formed by the second binder comprises borax.
In the example the sheet comprises pentaerythritol.
In the example, the ammonium polyphosphate has a chain length of more than 1000 orthophosphate ions.
A specific example of a sheet according to the invention comprises a nonwoven nonwoven fiberglass that has been produced by a wet process, according to the so-called wet laid process. This non-woven fiberglass comprises 160 grams per square meter of glass fibers of discrete length, which are bonded together by means of 20 grams per square meter of polyvinyl alcohol.
This nonwoven non-woven fiberglass was impregnated with melamine-formaldehyde resin to a weight of 420 grams per square meter. The melamine-formaldehyde resin comprises in dispersion ammonium polyphosphate (APP) with a chain length equal to or greater than 1000, so that the non-woven fiberglass impregnated with melamineformaldehyde comprises 48 grams per square meter of this ammonium polyphosphate. The melamine-formaldehyde resin further comprised borax as buffer. Triethylamine may also be used as buffer instead of borax. This impregnated non-woven fiberglass was dried to 5 to 8 percent residual moisture content, so that the melamine-formaldehyde resin is in B-stage. Optionally the melamine-formaldehyde resin may comprise pentaerythritol, but this is not necessary for the invention.
A second example of a sheet according to the invention comprises a nonwoven nonwoven fiberglass that has been produced by a wet process, according to the so-called wet laid process. This non-woven fiberglass comprises 57 grams per square meter of glass fibers of discrete length, which are bonded together by means of 10 grams per square meter of polyvinyl alcohol.
This nonwoven non-woven fiberglass was impregnated in two steps with melamine- formaldehyde resin to a weight of 400 grams per square meter. The melamine- formaldehyde resin comprises in dispersion ammonium polyphosphate (APP) with a chain length greater than or equal to 1000, so that the non-woven fiberglass impregnated with melamine-formaldehyde comprises 166 grams per square meter of this ammonium polyphosphate. The melamine-formaldehyde resin further comprised borax as a buffer. Triethylamine may also be used as a buffer instead of borax. This impregnated nonwoven fiberglass was dried to 5 to 8 percent residual moisture content, so that the melamine-formaldehyde resin is in B-stage. Optionally the melamine-formaldehyde resin may comprise pentaerythritol, but this is not necessary for the invention.
The laminate 1 further comprises a number of - for example three - layers of paper 16 impregnated with a resin. The sheet 10 is located between the decorative layer 12 and the one or more layers of paper 16. The layers of paper 16 may be layers of kraft paper, impregnated with phenol-formaldehyde resin.
The laminate 1 in Fig. 1 comprises a transparent or translucent wear layer 14, applied on the decorative layer. In the example, the wear layer 14 comprises a layer of paper impregnated by means of a melamine-formaldehyde resin. Optionally this wear layer comprises particles in order to increase the abrasion resistance of the wear layer.
The laminate may be produced by laying the various layers on one another and crosslinking the resins by means of pressure and elevated temperature.
Fig. 2 illustrates an example of a panel according to the invention. The panel comprises a substrate 18 and a laminate 1 such as in the first aspect of the invention, for example a laminate such as in Fig. 1. The reference numbers in Fig. 2 thus have the same meaning as the corresponding reference numbers in Fig. 1.
The substrate 18 may for example be or comprise a plurality of layers of paper bonded to each other by means of phenol-formaldehyde resin, a chipboard, an MDF board or an HDF board, preferably without this substrate comprising ammonium polyphosphate.
The present invention is by no means limited to the embodiments described above, but such products may be produced according to several variants while remaining within the scope of the present invention.

Claims

Claims
1.- A laminate, preferably wherein the laminate is or comprises a High Pressure
Laminate (HPL) or a Direct Pressure Laminate (DPL), the laminate comprises
- a decorative layer, wherein the decorative layer comprises a layer of paper impregnated with an aminoplast resin, preferably wherein the layer of paper is impregnated with melamine-formaldehyde resin; and
- a sheet; wherein the sheet comprises a non-woven fiberglass that comprises a polymer binder - preferably a thermoplastic binder or a thermosetting binder - and wherein the sheet comprises ammonium polyphosphate (APP); characterized in that according to a first option the ammonium polyphosphate is bonded with a second binder on one or on both sides to the non-woven fiberglass bonded with polymer binder, wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; or according to a second option the ammonium polyphosphate is bonded by means of the polymer binder in or to the non-woven fiberglass; and wherein the sheet comprises a second binder on both sides of the sheet; wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin.
2.- The laminate as claimed in claim 1, characterized in that the sheet comprises pentaerythritol, or in that the sheet does not comprise pentaerythritol.
3.- The laminate as claimed in any one of the preceding claims, characterized in that the ammonium polyphosphate comprises a chain length of more than 100 orthophosphate ions, and preferably comprises more than 500 orthophosphate ions, and more preferably comprises more than 750 orthophosphate ions, and even more preferably comprises more than 1000 orthophosphate ions.
4.- The laminate as claimed in any one of the preceding claims, wherein the ammonium polyphosphate is bonded with a second binder on one or on both sides to the non-woven fiberglass bonded with polymer binder, wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin, and in that this second binder forms a film, wherein this film comprises borax.
5.- The laminate as claimed in any one of the preceding claims, characterized in that the non-woven fiberglass is a wet laid non-woven fiberglass.
6.- The laminate as claimed in any one of the preceding claims, characterized in that the polymer binder is or comprises a polyvinyl alcohol.
7.- The laminate as claimed in any one of the preceding claims, characterized in that the decorative layer comprises a dyed or printed layer of paper.
8.- The laminate as claimed in any one of the preceding claims, characterized in that the laminate comprises one or more layers of paper impregnated with a resin, wherein the non-woven fiberglass is located between the decorative layer and the one or more layers of paper.
9.- The laminate as claimed in claim 8, characterized in that the one or more layers of paper are layers of kraft paper, preferably impregnated with a phenol-formaldehyde resin, more preferably impregnated with a phenol-formaldehyde resin that comprises melamine formaldehyde.
10.- The laminate as claimed in any one of claims 8-9, characterized in that the one or more impregnated layers of paper do not comprise ammonium polyphosphate.
11.- The laminate as claimed in any one of claims 8-10, characterized in that the laminate does not comprise any layers that comprise ammonium polyphosphate situated on the other side of the non-woven fiberglass than the side with the decorative layer. 19
12.- The laminate as claimed in any one of the preceding claims, characterized in that a transparent or translucent wear layer is applied on the decorative layer, for example by means of a layer of paper impregnated with resin - preferably with melamineformaldehyde resin - or by means of a resin coating, for example an acrylate or polyurethane acrylate coating layer; optionally wherein this wear layer comprises particles in order to increase the abrasion resistance of the wear layer.
13.- The laminate as claimed in any one of the preceding claims, characterized in that the weight of glass in the non-woven fiberglass is between 50 and 200 grams per square meter, preferably between 50 and 120 grams per square meter, e.g. 80 grams per square meter.
14.- The laminate as claimed in any one of the preceding claims, characterized in that the aminoplast resin is a melamine-formaldehyde resin or a melamine-urea- formaldehyde resin.
15.- The laminate as claimed in any one of the preceding claims, characterized in that the laminate comprises between 40 and 200 grams of ammonium polyphosphate per square meter, preferably between 40 and 180 grams of ammonium polyphosphate per square meter, preferably between 100 and 150 grams of ammonium polyphosphate per square meter.
16.- The laminate as claimed in any one of the preceding claims, characterized in that the ammonium polyphosphate is bonded with a second binder on one or on both sides to the binder-impregnated non-woven fiberglass, wherein this second binder is a thermosetting binder - preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin - wherein the second binder forms a film and in that borax and/or triethylamine or reaction products of triethylamine are incorporated in this film. 20
17.- The laminate as claimed in any one of the preceding claims, characterized in that the laminate is an HPL, wherein the decorative layer, the non-woven fiberglass and optionally other impregnated layers have been pressed together at elevated temperature and pressure.
18.- The laminate as claimed in claim 17, characterized in that the laminate is a
Continuous Pressure Laminate (CPL).
19.- A panel, characterized in that the panel comprises a substrate and a laminate as claimed in any one of the preceding claims.
20.- The panel as claimed in claim 19, characterized in that the substrate is or comprises a plurality of layers of paper bonded to each other by means of phenolformaldehyde resin, a chipboard, an MDF board or an HDF board.
21.- The panel as claimed in any one of the preceding claims 19-20, characterized in that the substrate does not comprise any ammonium polyphosphate.
22.- The panel as claimed in any one of the preceding claims 19-21, characterized in that the laminate is a High Pressure Laminate and is bonded to the substrate with a layer of glue.
23.- The panel as claimed in any one of the preceding claims 19 -21, characterized in that the laminate is a Direct Pressure Laminate.
24.- The panel as claimed in any one of the preceding claims 19-23, characterized in that the panel is a wall panel, a ceiling panel or a furniture panel.
25.- A sheet, wherein the sheet comprises a non-woven fiberglass that comprises a polymer binder - preferably a thermoplastic binder or a thermosetting binder - and wherein the sheet comprises ammonium polyphosphate (APP); characterized in that 21 according to a first option the ammonium polyphosphate is bonded with a second binder on one or on both sides to the non-woven fiberglass bonded with polymer binder, wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; or according to a second option the ammonium polyphosphate is bonded by means of the polymer binder in or to the non-woven fiberglass; and wherein the sheet comprises a second binder on both sides of the sheet; wherein this second binder is a thermosetting binder, preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; and wherein both according to the first option and according to the second option the second binder is in B-stage.
26.- The sheet as claimed in claim 25, characterized in that the sheet has a weight between 250-400 grams per square meter, preferably between 300-350 grams per square meter.
27.- The sheet as claimed in any one of the preceding claims 25-26, characterized in that the sheet comprises pentaerythritol, or in that the sheet does not comprise pentaerythritol.
28.- The sheet as claimed in any one of the preceding claims 25-27, characterized in that the ammonium polyphosphate comprises a chain length of more than 100 orthophosphate ions, and preferably comprises more than 500 orthophosphate ions, and more preferably comprises more than 750 orthophosphate ions, and even more preferably comprises more than 1000 orthophosphate ions.
29.- The sheet as claimed in any one of the preceding claims 25-28, characterized in that the second binder forms a film and this film comprises borax.
30.- The sheet as claimed in any one of the preceding claims 25-29, characterized in that the non-woven fiberglass is a wet laid non-woven fiberglass. 22
31.- The sheet as claimed in any one of the preceding claims 25-30, characterized in that the polymer binder is or comprises a polyvinyl alcohol.
32.- The sheet as claimed in any one of the preceding claims 25-31, characterized in that the weight of glass in the non-woven fiberglass is between 50 and 200 grams per square meter, preferably between 50 and 120 grams per square meter, e.g. 80 grams per square meter.
33.- The sheet as claimed in any one of the preceding claims 25-32, characterized in that the sheet comprises between 40 and 200 grams of ammonium polyphosphate per square meter, preferably comprises between 40 and 180 grams of ammonium polyphosphate per square meter, preferably between 100 and 150 grams of ammonium polyphosphate per square meter.
34.- The sheet as claimed in any one of the preceding claims 25-33, characterized in that the ammonium polyphosphate is bonded with a second binder on both sides to the binder-impregnated non-woven fiberglass, wherein this second binder is a thermosetting binder - preferably wherein the second binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin - wherein borax and/or triethylamine or reaction products of triethylamine are incorporated in the film formed by the second binder.
35.- A method of producing a sheet, optionally a sheet as claimed in any one of the preceding claims 25-34; wherein the method comprises the step of impregnating a non-woven fiberglass in a bath; wherein the bath comprises a thermosetting binder, preferably wherein the thermosetting binder is a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin; and wherein the bath comprises ammonium polyphosphate (APP) or wherein ammonium polyphosphate (APP) is spread on the wet non-woven fiberglass impregnated with thermosetting binder; and wherein the method comprises the step of drying to B-stage after impregnation in the bath. 23
36.- The method as claimed in claim 35, characterized in that the non-woven fiberglass comprises a polymer binder - preferably a thermoplastic binder or a thermosetting binder.
37.- The method as claimed in claim 36, characterized in that the polymer binder is or comprises a polyvinyl alcohol.
38.- The method as claimed in any one of the preceding claims 35-37, characterized in that in the method, a sheet is produced with a weight between 250-400 grams per square meter, more preferably between 300-350 grams per square meter.
39.- The method as claimed in any one of the preceding claims 35-38, characterized in that the non-woven fiberglass is a wet laid non-woven fiberglass.
40.- The method as claimed in any one of the preceding claims 35-39, characterized in that the weight of glass in the non-woven fiberglass is between 50 and 200 grams per square meter, preferably between 50 and 120 grams per square meter, e.g. 80 grams per square meter.
41.- The method as claimed in any one of the preceding claims 35-40, characterized in that the bath comprises pentaerythritol; or in that the bath does not comprise pentaerythritol.
42.- The method as claimed in any one of the preceding claims 35-41, characterized in that the ammonium polyphosphate comprises a chain length of more than 100 orthophosphate ions, preferably comprises more than 500 orthophosphate ions, more preferably comprises more than 750 orthophosphate ions, and even more preferably comprises more than 1000 orthophosphate ions. 24
43.- The method as claimed in any one of the preceding claims 35-42, characterized in that the bath comprises a buffer, for example borax or triethylamine or reaction products of triethylamine.
44.- The method as claimed in any one of the preceding claims 35-43, characterized in that in the method the non-woven fiberglass is impregnated so that the sheet produced comprises between 40 and 200 grams of ammonium polyphosphate per square meter, preferably between 40 and 180 grams of ammonium polyphosphate per square meter, more preferably between 100 and 150 grams of ammonium polyphosphate per square meter.
PCT/IB2022/061209 2021-11-30 2022-11-21 Flame-retardant laminate WO2023100025A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP22809530.3A EP4440831A1 (en) 2021-11-30 2022-11-21 Flame-retardant laminate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE20215925A BE1029969B1 (en) 2021-11-30 2021-11-30 Flame retardant laminate
BE2021/5925 2021-11-30

Publications (1)

Publication Number Publication Date
WO2023100025A1 true WO2023100025A1 (en) 2023-06-08

Family

ID=78829432

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2022/061209 WO2023100025A1 (en) 2021-11-30 2022-11-21 Flame-retardant laminate

Country Status (3)

Country Link
EP (1) EP4440831A1 (en)
BE (1) BE1029969B1 (en)
WO (1) WO2023100025A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006111458A1 (en) 2005-04-18 2006-10-26 Owens-Corning Intellectual Capital, Llc Fire retardant laminate
CN101175634A (en) * 2005-04-18 2008-05-07 欧文斯科宁知识产权资产有限公司 Non-combustible high pressure laminate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006111458A1 (en) 2005-04-18 2006-10-26 Owens-Corning Intellectual Capital, Llc Fire retardant laminate
CN101175634A (en) * 2005-04-18 2008-05-07 欧文斯科宁知识产权资产有限公司 Non-combustible high pressure laminate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "Ammonium polyphosphate of Flame Retardant product from SinoHarvest Ammonium polyphosphate manufacturer", 22 May 2010 (2010-05-22), XP055951148, Retrieved from the Internet <URL:https://web.archive.org/web/20100522123855/http://www.sinoharvest.com/products/Ammonium-Polyphosphate.shtml> [retrieved on 20220812] *

Also Published As

Publication number Publication date
BE1029969A1 (en) 2023-06-21
BE1029969B1 (en) 2023-06-28
EP4440831A1 (en) 2024-10-09

Similar Documents

Publication Publication Date Title
JP3044203B2 (en) Method of coating melamine resin on laminated paper
KR100493535B1 (en) Flame-retardant or incombustible decorative laminated sheet
CN107848263B (en) Decorative sheet
US3511748A (en) Decorative laminate having superior fire retardant properties
US12276117B2 (en) Board and floor panel based on such board
CN111806002A (en) Composite board made of wood material
KR20160138243A (en) Decorative board
EP0249583B1 (en) Decorative plastics laminate and method for its manufacture
US6379786B1 (en) Ligneous finishing material
US20060216536A1 (en) Synthetic resin film for laminates and method of producing same
EP4440831A1 (en) Flame-retardant laminate
US4165409A (en) Method of fabricating wood composite panels having enhanced fire retardancy
US20240102248A1 (en) Use of non-halogen fire retardant composition for indirect fire protection layers on substrates
RU2471632C2 (en) New composite materials, methods of their production and application
CN117295803A (en) Use of halogen-free flame retardant compositions for indirect flame-proofing layers on substrates
US20240034888A1 (en) Non-halogen fire-retardant composition and use of said composition for direct and indirect fire protection layers on substrates
FI131242B1 (en) A multi-layered building element and a use thereof
US20240165924A1 (en) Panels and method for producing panels
WO2025133448A1 (en) A multi-layered building element and a use thereof
Çiçekler et al. Resin impregnation of decor papers and comparison of physical properties
TUTUS et al. EFFECTS OF RESIN IMPREGNATION RATES ON PHYSICAL PROPERTIES OF BALANCE PAPERS
EP4556214A1 (en) Nonwoven with new thermoplastic binder
CN115284406A (en) Method for manufacturing metal wire fiber wood composite floor
CICEKLER et al. RES) N) MPREGNAT) ON OF DECOR PAPERS AND COMPAR) SON OF P (YS) CAL PROPERT) ES
EP2560812A1 (en) Composite material, method of producing the same and the use thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22809530

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2022809530

Country of ref document: EP

Effective date: 20240701