Polyurethane composite material, laminated product containing polyurethane composite material and method for producing same

Abstract

The present invention relates to a novel polyurethane (PU) composite, a method for producing the PU composite, and a coated article comprising the PU composite. The PU composite comprises 35-75% by weight of reinforcing fibers and 25-65% by weight of polyurethane foam, based on the total weight of the PU composite, where the reinforcing fibers comprise 75-100% by weight of reinforcing fibers in the form of a continuous phase and 0-25% by weight of reinforcing fibers in the form of a discontinuous phase, based on the total weight of the reinforcing fibers. The present invention further relates to a laminated product comprising at least one insulating layer and at least two polyurethane composites arranged on either side of the insulating layer, a method for producing the laminated product, and a coated article for a battery system comprising the laminated product.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of International Application No. PCT / CN2021 / 117427, filed September 9, 2021, the entire contents of which are incorporated herein by reference.

[0002] Technical Field The present invention relates to a novel polyurethane (PU) composite material, a method for producing the PU composite material, and a coated article comprising the PU composite material. The PU composite material comprises 35-75% by weight of reinforcing fibers and 25-65% by weight of polyurethane foam, based on the total weight of the PU composite material, where the reinforcing fibers comprise 75-100% by weight of reinforcing fibers in the form of a continuous phase and 0-25% by weight of reinforcing fibers in the form of a discontinuous phase, based on the total weight of the reinforcing fibers. The present invention further relates to a laminated product comprising at least one insulating layer and a polyurethane composite material arranged on both sides of the insulating layer, a method for producing the laminated product, and a coated article comprising the laminated product.

[0003] Background technology With the development of electric vehicles, more and more attention is being paid to lightweight design and battery capacity limitations. Currently, stamped metal sheets are mainly used as the top cover of the battery pack to protect the battery components in the battery pack. Although metal materials exhibit good mechanical properties, they have high density and therefore high mass of the parts; therefore, it is urgent to provide a new lightweight, thin and flame-retardant part to replace the metal top cover.

[0004] The prior art discloses injection-molded parts based on polypropylene or polyamide as the top cover of the battery pack. However, it is difficult to realize very large size parts with such polypropylene or polyamide material injection molding solutions, and the injection molding requires high mold costs, high injection pressure and injection temperature. To date, there is no literature or patent that discloses or suggests that spray transfer molding (STM) products or long fiber injection molding (LFI) products, such as the PU composite material thus obtained, can be used as the top cover of the battery pack.

[0005] For example, US Patent Application Publication No. 2019 / 0153185 discloses a sandwich component including a polyurethane foam core and two building material plates, which are used as non-load-bearing wall elements, exterior wall cladding, and ceiling elements. In particular, it is disclosed that the building plate may further include fibers, fabrics, or reinforcements that improve the tensile strength of the building material plate. Nevertheless, it is not disclosed or suggested that the polyurethane foam core can be modified to be specifically applied in the battery field, for example as a top cover for a battery pack. Furthermore, it is understood by those skilled in the art that polyurethane foam in the building field is relatively thick, which prevents its use as a top cover for a thinner battery pack.

[0006] Furthermore, the prior art discloses a sheet molding compound (SMC) process for producing polyurethane foam sheets, which is characterized by impregnating chopped glass fibers with resin. However, this SMC process usually suffers from the disadvantages of high density, thick components, non-uniform distribution of reinforcing glass fibers in the final components, and high costs of post-processing steps.

[0007] Meanwhile, China Patent Publication No. 107437631 discloses a battery module containing a plurality of single batteries, a frame and a protective plate. The protective plate contains an expandable graphite (EG) plate and an insulating sealing film, the EG plate contains a substrate formed from an adhesive and EG particles dispersed in the substrate, and the sealing film is a polyimide (PI) film or a polypropylene (PP) film. US Patent Publication No. 20080020270 describes a secondary battery for mobile devices, which includes a film ("safety film") containing EG and polyurethane, and a substrate film selected from polyurethane and polyethylene terephthalate. However, the prior art only provides products with limited EG content, and therefore the heat insulation effect is also limited.

[0008] Therefore, there is a continuing need to provide composite materials that are light-weight, thin, have good mechanical properties and flame retardant properties, and at the same time can be manufactured in a cost-effective manner. Furthermore, there is a need for composite materials that are easily prepared using a wide range of raw materials and provide coated articles that have excellent electromagnetic interface (EMI) shielding performance and the advantages described above for composite materials. In addition to the advantages described above for composite materials, there is also a need to provide products that have excellent thermal insulation properties.

[0009] Summary of the Invention The object of the present invention is to overcome the above-mentioned problems of the prior art and to provide a composite material which is light in weight, has good mechanical strength, is flame retardant and has excellent voltage resistance, and at the same time can be prepared in a cost-effective manner.

[0010] Surprisingly, the inventors have discovered that said object is achieved by providing a polyurethane (PU) composite material comprising 35-75% by weight of reinforcing fibers and 25-65% by weight of polyurethane foam, relative to the total weight of the polyurethane (PU) composite material, Here, the polyurethane foam is defined as follows: (a) at least one isocyanate or isocyanate prepolymer; an isocyanate component consisting of (b) at least one polyol that is reactive towards isocyanates; (c) optionally a chain extender and / or a crosslinker; (d) flame retardants; (e) optionally a filler; (f) foaming agents; (g) Catalysts; and (h) optionally additives and / or auxiliaries A polyol component consisting of obtained from a two-component reaction system comprising The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers and natural fibers; and The reinforcing fibers include 75 to 100 mass% of reinforcing fibers in the form of a continuous phase and 0 to 25 mass% of reinforcing fibers in the form of a discontinuous phase, based on the total mass of the reinforcing fibers; It has been found that this can be achieved by the polyurethane (PU) composite material.

[0011] In a further aspect, the present invention relates to a method for producing said PU composite material, said method comprising the steps of: 1) providing reinforcing fibers in the form of a continuous phase; 2) preparing a polyol component by mixing the following materials in a tank at a temperature of 20-80°C: (b) at least one polyol that is reactive towards isocyanates; (c) optionally a chain extender and / or a crosslinker; (d) flame retardants; (e) optionally a filler; (f) foaming agents; (g) Catalysts; and (h) optionally additives and / or auxiliaries; 3) mixing the polyol component obtained in step 2) with the isocyanate component and optionally reinforcing fibers in the form of a discontinuous phase at a temperature of 20-80° C. to obtain a mixture; 4) spraying or extruding the mixture obtained in step 3) by means of a first nozzle or extrusion head onto the reinforcing fibers in the form of a continuous phase provided in step 1) and, optionally, spraying the reinforcing fibers in the form of a discontinuous phase by means of a second nozzle onto the reinforcing fibers in the form of a continuous phase provided in step 1) to obtain a sprayed or extruded product; 5) hot pressing the sprayed or injected product obtained in step 4) in a mold having a temperature of 40-180°C under a hot press clamping force of 100-2000 tons; and 6) demolding and optional trimming; Including, The polyurethane composite material obtained in step 6) contains 35 to 75% by mass of reinforcing fibers and 25 to 65% by mass of polyurethane foam, based on the total mass of the polyurethane composite material; The reinforcing fibers include 75 to 100 mass % of reinforcing fibers in the form of a continuous phase and 0 to 25 mass % of reinforcing fibers in the form of a discontinuous phase, based on the total mass of the reinforcing fibers; The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers.

[0012] Surprisingly, it has been found in the present application that the PU composite material or the PU composite material produced by the method exhibits reduced weight, good mechanical strength, flame retardancy and excellent voltage resistance. Moreover, the method is carried out in a robust and simple manner. Likewise, the PU composite material is obtained in a cost-effective manner.

[0013] In yet another aspect, the present invention relates to a coated article comprising at least one of said PU composite materials or a PU composite material produced by said method.

[0014] Another object of the present invention is to provide a laminated product which has light weight, good mechanical strength, flame retardancy and good thermal insulation properties.

[0015] Surprisingly, the inventors have found that this object can be achieved by a laminate product comprising at least one insulating layer and at least two polyurethane composite layers as described above arranged on either side of the insulating layer, wherein the insulating layer comprises a binder and an insulating material dispersed in the binder.

[0016] In a further aspect, the present invention provides a method for producing a method for treating a cancer cell comprising the steps of: 1) i) Mix the insulation material and binder; ii) applying the mixture of step i) to a surface of a substrate and allowing the mixture to cure; iii) Optionally removing the substrate providing a heat insulating layer by 2) providing reinforcing fibers in the form of a continuous phase arranged on both sides of the insulation layer obtained in step 1); 3) The following materials: (b) at least one polyol that is reactive towards isocyanates; (c) optionally a chain extender and / or a crosslinker; (d) flame retardants; (e) optionally a filler; (f) foaming agents; (g) Catalysts; and (h) optionally additives and / or auxiliaries in a tank at a temperature of 20 to 80° C. to prepare a polyol component; 4) mixing the polyol component obtained in step 3) with an isocyanate component and optionally reinforcing fibers in the form of a discontinuous phase at a temperature of 20-80° C. to obtain a mixture; 5) spraying or extruding the mixture obtained in step 4) by means of a first nozzle or extrusion head onto the reinforcing fibers in the form of a continuous phase arranged on both sides of the insulation layer provided in step 2), and optionally spraying reinforcing fibers in the form of a discontinuous phase by means of a second nozzle onto the reinforcing fibers in the form of a continuous phase provided in step 2) to obtain a sprayed or extruded product; 6) hot pressing the sprayed or injected product obtained in step 5) in a mold having a temperature of 40-180°C under a hot press clamping force of 100-2000 tons; and 7) Demolding and optionally trimming, thereby obtaining a laminated product comprising a polyurethane composite material disposed on both sides of the insulating layer. a method for producing the laminated product, comprising: Here, the polyurethane composite material contains 35 to 75 mass% of reinforcing fiber and 25 to 65 mass% of polyurethane foam based on the total mass of the polyurethane composite material, The reinforcing fibers comprise 75-100% by mass of reinforcing fibers in the form of a continuous phase and 0-25% by mass of reinforcing fibers in the form of a discontinuous phase, based on the total mass of the reinforcing fibers; and The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers.

[0017] Surprisingly, it has been found in the present application that the laminated product, or the laminated product produced by the method, exhibits a low weight, good mechanical strength, flame retardancy, and excellent voltage resistance. Moreover, the method is carried out in a robust and simple manner. Likewise, the laminated product is obtained cost-effectively.

[0018] In yet another aspect, the present invention relates to a coated article comprising at least one of the laminated products described above, or a laminated product produced by the method described above. [Brief description of the drawings]

[0019] [Figure 1] FIG. 1 shows the STM process for producing PU composites. [Diagram 2] FIG. 2 shows the LFI process for producing PU composites. [Diagram 3] FIG. 3 shows a coated article comprising a PU composite and a metal sheet. [Figure 4]FIG. 4 shows a laminated product comprising two PU composite layers with a thermal insulation layer between them. [Diagram 5] FIG. 5 shows a method for producing a thermal insulation layer. [Figure 6] FIG. 6 illustrates a method for producing a laminated product.

[0020] Detailed Description of the Invention Unless otherwise defined, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs. As used herein, the following terms have the following meanings unless otherwise specified:

[0021] As used herein, the articles "a" and "an" are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, "an element" means one element or more than one element.

[0022] As used herein, the term "comprising" also encompasses the term "consisting of."

[0023] Unless otherwise specified, all percentages (%) are "percent by weight."

[0024] Unless otherwise specified, temperature refers to room temperature and pressure refers to ambient pressure.

[0025] As used herein, the term "reinforcing fibers in the form of a continuous phase" refers to a fibrous layer in which the fibers that make up the fibrous layer are bonded or interlocked to form an integral layer.

[0026] As used herein, the term "reinforcing fibers in the form of a discontinuous phase" refers to fibers that are not bonded or integrated together.

[0027] I. PU composite material In one aspect, the present invention provides a polyurethane (PU) composite material, the polyurethane composite material comprising 35-75% by weight of reinforcing fiber and 25-65% by weight of polyurethane foam, based on the total weight of the polyurethane (PU) composite material; Polyurethane foam is as follows: (a) at least one isocyanate or isocyanate prepolymer; an isocyanate component consisting of (b) at least one polyol that is reactive towards isocyanates; (c) optionally a chain extender and / or a crosslinker; (d) flame retardants; (e) optionally a filler; (f) foaming agents; (g) Catalysts; and (h) optionally additives and / or auxiliaries A polyol component consisting of obtained from a two-component reaction system comprising The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers; and The reinforcing fibers include 75 to 100 mass% of reinforcing fibers in the form of a continuous phase and 0 to 25 mass% of reinforcing fibers in the form of a discontinuous phase, based on the total mass of the reinforcing fibers; This relates to polyurethane (PU) composite materials.

[0028] In one embodiment, the reinforcing fibers are impregnated with a polyurethane foam.

[0029] In one embodiment, the reinforcing fibers in the form of a continuous phase are in the form of a mat, a woven fabric, or a combination thereof. In a particular embodiment, the reinforcing fibers in the form of a continuous phase are aggregate rovings E512 available from China Jushi Co.Ltd. In the present invention, the term "mat" refers to a material in the form of a felt, a thin fabric, a relatively thin sheet, a knitted form, etc. In one embodiment, the mat is formed by a method known in the art, such as a conventional method using warp and weft threads or an electrospinning method. Based on this, it will be understood that the reinforcing fibers in the form of a continuous phase may be in the form of a veil mat, a chopped strand mat, a woven fabric, a nonwoven fabric, a fiber fabric, a stitch mat, etc.

[0030] In one embodiment, the reinforcing fibers in the continuous phase have a density of 200 to 1600 grams per square meter, preferably 400 to 900 grams per square meter.

[0031] In one embodiment, the PU composite material comprises a reinforcing fiber mat in the form of a continuous phase of 1 to 4 layers of mat, woven fabric or a combination thereof, preferably 1 to 4 layers, such as 1, 2, 3, or 4 layers.

[0032] In one embodiment, the PU composite material comprises reinforcing fibers in the form of a discontinuous phase. In one embodiment, the reinforcing fibers in the form of a discontinuous phase have a length of 6-100 mm, preferably 8-80 mm, more preferably 10-50 mm, and even more preferably 12-25 mm. In a particular embodiment, the reinforcing fibers in the form of a discontinuous phase are aggregate rovings E440 available from China Jushi Co.Ltd.

[0033] In one embodiment, the PU composite has a viscosity of 2.2 g / mm 3 Less than 1.8g / mm 3 Less than 1.6g / mm 3 less than 1.5g / mm 3 less than 1.3 g / mm 3Less than 1.2 g / mm 3 has a density of less than .

[0034] In one embodiment, the PU composite material is made in the form of a sheet having a thickness of 0.5-10 mm, preferably 1-5 mm, more preferably 1-3 mm, even more preferably 1-2 mm.

[0035] In one embodiment, the polyurethane composite comprises a flame retardant (d) selected from the group consisting of expandable graphite, red phosphorus, ammonium polyphosphate, triethyl phosphate, tris(2-chloropropyl) phosphate, melamine, expandable graphite (EG), red phosphorus, ammonium polyphosphate, tris(1-chloro-2-propyl) phosphate (TCPP), triethyl phosphate (TEP), chlorine and bromine containing polyols such as epichlorohydrin, chlorendic anhydride, trichlorobutylene oxide (TCBO), phosphorus containing polyols such as esters of orthophosphoric acid, esters of phosphoric acid, phosphanate polyols, phosphine oxide polyols, and phosphoramide polyols.

[0036] In one embodiment, the PU composite material has a tensile strength, determined according to GB / T1447-2005, of at least 90 MPa, preferably at least 95 MPa, more preferably at least 100 MPa, even more preferably at least 120 MPa, and most preferably at least 130 MPa.

[0037] In one embodiment, the PU composite has a flexural strength, determined according to GB / T1449-2005, of at least 180 MPa, preferably at least 185 MPa, more preferably at least 190 MPa, even more preferably at least 200 MPa, and most preferably at least 230 MPa.

[0038] In one embodiment, the PU composite material passes the UL94 V0 grade for fire resistance test. In one embodiment, the PU composite material passes the UL94 5VA fire resistance test.

[0039] Polyurethane The preparation of PU composites uses an "isocyanate component" and a "polyol component" (hereinafter also referred to as "resin component" or "resin"), the "polyol component" being a mixture of an isocyanate-reactive polyol (b), optionally a chain extender and / or crosslinker (c), a flame retardant (d), optionally a filler (e), a blowing agent (f), a catalyst (g), and optionally an auxiliary and additive (h), and the "isocyanate component" being at least one isocyanate or isocyanate prepolymer (a). The polyol component reacts with the isocyanate to form a urethane bond. Such a system is disclosed, for example, in U.S. Pat. No. 4,218,543.

[0040] It should be noted that in the present invention, the polyol component does not include reinforcing fibers, i.e., both continuous and discontinuous.

[0041] In a preferred embodiment, the "isocyanate component" and the "polyol component" are impingement mixed and sprayed or injected into a mold at about atmospheric pressure, after which the mold is closed. The mold is preheated to 40-180°C, preferably 70-150°C, more preferably 90-130°C, and optionally includes an insert (e.g., a metal sheet, metal foil, or solid flame retardant layer) on the mold surface. The raw material is sprayed or injected uniformly onto the fiber fabric in the mold, after which the molded part is removed from the mold, typically after 1-15 minutes, preferably 90 seconds to 10 minutes, more preferably 2-8 minutes.

[0042] Isocyanate or isocyanate prepolymer (a) The isocyanate component used to prepare the polyurethanes of the present invention includes any of the isocyanates known to prepare polyurethanes, including aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, such as tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), cycloisocyanates, ... These include hexane 1,4-diisocyanate, 1-methylcyclohexane 2,4- and / or 2,6-diisocyanate and / or dicyclohexylmethane 4,4'-, 2,4'- and 2,2'-diisocyanate, diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), polymeric MDI, naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and / or 2,6-diisocyanate (TDI), 3,3'-dimethyldiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and / or phenylene diisocyanate. It is particularly preferred to use 2,2'-, 2,4'- and / or 4,4'-diisocyanate, and polymeric MDI.

[0043] Other possible isocyanates are listed, for example, in "Kunststoffhandbuch, Band 7, Polyurethane" [Plastics handbook, volume 7, Polyurethanes], Carl Hanser Verlag, 3rd edition, 1993, chapters 3.2 and 3.3.2.

[0044] In addition, the isocyanate component may be used in the form of an isocyanate prepolymer. The isocyanate prepolymer is obtained, for example, by reacting said isocyanate with an additional polyol (a') at a temperature of 30 to 100°C, preferably about 80°C. For preparing the prepolymer used according to the invention, uretonimine-modified MDI and commercially available polyols based on polyesters, such as those derived from adipic acid or polyethers, such as those derived from ethylene oxide and / or propylene oxide, are preferred. For preparing the prepolymer used according to the invention, polyols derived from 4,4'-MDI and ethylene oxide and / or propylene oxide are preferred.

[0045] The additional polyols (a') are known to those skilled in the art and are described, for example, in "Kunststoffhandbuch [Plastics handbook], Volume 7, Polyurethane [Polyurethanes]", Carl Hanser Verlag, 3rd Edition 1993, chapter 3.1.

[0046] The ether-based prepolymers are preferably obtained by reacting isocyanates, particularly preferably 4,4'-MDI, with di- to tri-functional polyoxypropylene polyols and / or polyoxypropylene-polyoxyethylene polyols. They are usually prepared by the generally known base-catalyzed addition of propylene oxide, alone or in mixtures with ethylene oxide, to H-functional, especially OH-functional starting materials. The starting materials used are, for example, water, ethylene glycol or propylene glycol, and glycerol or trimethylolpropane. Furthermore, polymetallic cyanide compounds, known as DMC catalysts, can also be used as catalysts. For example, the polyethers described below under component (b) may be used as additional polyol (a').

[0047] When ethylene oxide / propylene oxide mixtures are used, ethylene oxide is preferably used in an amount of 10-50% by weight, based on the total amount of alkylene oxide. The alkylene oxide may be incorporated in blocks or as a random mixture. It is particularly preferred to incorporate ethylene oxide end blocks ("EO caps") in order to increase the content of more reactive primary OH end groups. The number average molecular weight of polyol (a') is preferably in the range of 1750-5500 g / mol.

[0048] If appropriate, a conventional chain extender or crosslinker is added to the additional polyol mentioned in the preparation of the isocyanate prepolymer. The conventional chain extender or crosslinker may be the same as those described in c) below. It is particularly preferred to use dipropylene glycol, tripropylene glycol or monoethylene glycol (MEG) as the chain extender or crosslinker.

[0049] (b) isocyanate-reactive polyol The isocyanate-reactive polyol (b) may be any of the polyols useful in the art for the preparation of polyurethanes and having at least two reactive hydrogen atoms. For example, it is possible to use polyether polyamines and / or polyols selected from the group of polyether polyols and polyester polyols, or mixtures thereof.

[0050] The polyol preferably used is a polyether polyol having a mass average molecular weight of 200 to 10,000, preferably 300 to 8000, more preferably 500 to 6000, and most preferably 2500 to 3500, and an OH value of 20 to 1200 mgKOH / g, preferably 30 to 1000 mgKOH / g, and more preferably 40 to 500, and / or a polyester polyol having a molecular weight of 350 to 2000, preferably 350 to 650, and an OH value of 60 to 650 mgKOH / g, preferably 120 to 310 mgKOH / g. The following polyols are preferred in the present invention: LUPRANOL® 2095 (BASF), LUPRANOL® 2090 (BASF), LUPRANOL 3505 / 1 (BASF), LUPRAPHEN® 3905 (BASF), LUPRAPHEN® 3907 (BASF), LUPRAPHEN® 3909 (BASF), STEPANPOL® PS3152, PS2412, PS1752, CF6925 (Stepan Company).

[0051] The polyether polyols used in the present invention can be prepared by known methods, for example, from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical, using an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, or via anionic polymerization using an alkali metal alcoholate, such as sodium methoxide, sodium or potassium ethoxide, or potassium propoxide, as catalyst, with the addition of at least one starter molecule containing 2 to 8 reactive hydrogen atoms, or via cationic polymerization using a Lewis acid, such as antimony pentachloride, boron fluoride etherate, etc., or bleaching earth as catalyst.

[0052] Examples of suitable alkylene oxides are tetrahydrofuran, propylene 1,2-oxide, butylene 1,2-oxide or butylene 2,3-oxide, styrene oxide, preferably ethylene oxide and propylene 1,2-oxide. The alkylene oxides can be used individually, alternatingly in succession or as mixtures.

[0053] Examples of starter molecules which can be used are water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic organic dicarboxylic acids, N-mono-, N,N- and N,N'-dialkyl-substituted diamines, optionally having 1 to 4 carbon atoms in the alkyl group, such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, phenylenediamine, 2,3-, 2,4- and 2,6-tolylenediamine, and 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane.

[0054] The polyester polyols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, and polyhydric alcohols. Examples of dicarboxylic acids that can be used are aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, and sebacic acid, and aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid, and terephthalic acid. The dicarboxylic acids can be used individually or in the form of mixtures, for example in the form of a mixture of succinic acid, glutaric acid, and adipic acid. Examples of polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6, carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol, 1,3-propanediol, and dipropylene glycol, triols having 3 to 6 carbon atoms, such as glycerin, trimethylolpropane, and pentaerythritol as a highly functional alcohol. The polyhydric alcohols can be used alone or optionally mixed with one another, according to the desired properties.

[0055] The amount of polyether polyol and / or polyester polyol is preferably from 0 to 40% by mass, particularly preferably from 15 to 35% by mass, based on the total mass of the resin.

[0056] Chain extenders and / or crosslinkers (c) Chain extenders and / or crosslinkers (c) which may be used are preferably substances having a molar mass of less than 500 g / mol, particularly preferably between 60 and 400 g / mol, where the chain extenders have two hydrogen atoms reactive towards isocyanates and the crosslinkers have three hydrogen atoms reactive towards isocyanates. These may be used alone or, preferably, in the form of a mixture. It is preferred to use diols and / or triols having a molecular weight of less than 500, in particular between 60 and 400, in particular between 60 and 350. Examples that may be used are aliphatic, cycloaliphatic and / or araliphatic diols having 2 to 14, preferably 2 to 10, carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, 1,2-, 1,3-, 1,4-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, tripropylene glycol, diethanolamine, or triols such as 1,2,4- or 1,3,5-trihydroxycyclohexane, glycerol and trimethylolpropane. The chain extenders and / or crosslinkers (c) are preferably selected from ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol and glycerin.

[0057] The amount of chain extender and / or crosslinker c), if present, is preferably 0 to 50% by weight, particularly preferably 10 to 40% by weight, based on the total weight of the resin.

[0058] Flame retardants (d) Flame retardants (d) that can be used are additive flame retardants and reactive flame retardants, or a combination thereof. Additive flame retardants are monomer molecules that are not chemically bound to the polymer. Additive flame retardants can be in the form of solid flame retardants, liquid flame retardants, or a combination thereof. Commercially available additive flame retardants are tris(2-chloropropyl)phosphate, melamine, expandable graphite (EG), red phosphorus, ammonium polyphosphate, tris(1-chloro-2-propyl)phosphate (TCPP), triethyl phosphate (TEP). Reactive flame retardants are generally polyols containing halogens and / or phosphorus. Flame retardant polyols have terminal hydroxyl groups that can react with polyisocyanates in the PU synthesis. Halogen-containing FR polyols can be chlorine- and bromine-containing polyols, such as epichlorohydrin, chlorendic anhydride, and trichlorobutylene oxide (TCBO); phosphorus-containing polyols, such as esters of orthophosphoric acid, esters of phosphoric acid, phosphanate polyols, phosphine oxide polyols, phosphoramide polyols.

[0059] For the purpose of flame retardancy, the total amount of the flame retardant is preferably in the range of 5 to 30% by mass, more preferably 10 to 25% by mass, based on the total mass of the resin.

[0060] Filler (e) The filler that can be used is the usual organic or inorganic filler known per se.Specific examples that may be mentioned are inorganic fillers, such as silicate minerals, metal oxides, such as alumina, titanium oxide and iron oxide.In the present invention, the filler has an average particle size of less than 600 μm, preferably less than 500 μm, more preferably less than 400 μm.Filler (e) is preferably selected from titanium oxide and iron oxide.

[0061] The amount of the filler is 0-30% by mass, preferably 0-15% by mass, based on the total mass of the resin. The mass ratio of the flame retardant (d) to the filler (e) is in the range of 0.1-10, preferably 0.5-2.

[0062] The filler can function, for example, to reduce the coefficient of thermal expansion of the polyurethane foam, which is greater than that of the metal, and thus match this coefficient to that of the metal, which is particularly advantageous for durable adhesion between the metal sheet and the polyurethane core layer, as it results in lower stresses between the layers when subjected to thermal loads.

[0063] In the present invention, the filler (e) does not include reinforcing fibers, i.e., reinforcing fibers in continuous and discontinuous form, in other words, the polyol component does not include reinforcing fibers, i.e., reinforcing fibers in continuous and discontinuous form.

[0064] Foaming agent (f) The blowing agent (f) used according to the present invention preferably comprises water. The blowing agents (f) that can be used can include not only water but also other chemical and / or physical blowing agents in the art. Chemical blowing agents are compounds that form gaseous products by reaction with isocyanates, for example water or formic acid. Physical blowing agents are compounds that are dissolved or emulsified in the starting materials for polyurethane production and that evaporate under the conditions of polyurethane formation. For example, these are hydrocarbons, halogenated hydrocarbons, and other compounds, such as perfluorinated alkanes, for example perfluorohexane, fluorochlorocarbons, and ethers, esters, ketones and / or acetals. In a preferred embodiment, water is used as the only blowing agent (f). In this case, the polyurethane foam according to the present invention is a water-blown polyurethane spray foam. There is no particular limitation regarding the water. Mineral water, deionized water, or tap water may be used.

[0065] The amount of the foaming agent is 0 to 5% by mass, preferably 0.1 to 3% by mass, based on the total mass of the resin.

[0066] Catalyst (g) As catalyst (g), any compound that accelerates the isocyanate-polyol reaction can be used. Such compounds are known and are described, for example, in "Kunststoffhandbuch, volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 3.4.1. These include amine-based catalysts and organometallic catalysts.

[0067] As the organometallic compound catalyst, for example, an organotin compound such as a tin(II) salt of an organic carboxylic acid, for example, tin(II) acetate, tin(II) octanoate, tin(II) ethylhexanoate, tin(II) laurate, and a dialkyltin(IV) salt of an organic carboxylic acid, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate, and a bismuth carboxylate, for example, bismuth(III) neodecanoate, bismuth 2-ethylhexanoate, bismuth octanoate, or an alkali metal salt of a carboxylic acid, for example, potassium acetate or potassium formate, can be used.

[0068] As catalyst (g), it is preferable to use an amine catalyst, such as N,N,N',N'-tetramethyldipropylenetriamine, 2-[2-(dimethylamino)ethyl-methylamino]ethanol, N,N,N'-trimethyl-N'-2-hydroxyethyl-bis-(aminoethyl)ether, bis(2-dimethylaminoethyl)ether, N,N,N,N,N-pentamethyldiethylenetriamine, N,N,N-triethylaminoethoxyethanol, dimethylcyclohexylamine, trimethylhydroxyethylethylenediamine, dimethylbenzylamine, triethylamine, triethylenediamine, pentamethyldipropylenetriamine, dimethylethanolamine, N-methylimidazole, N-ethylimidazole, tetramethylhexamethylenediamine, tris(dimethylaminopropyl)hexahydrotriazine, dimethylaminopropylamine, N-ethylmorpholine, diazabicycloundecene and diazabicyclononene. Examples that may be mentioned here are Jeffcat ZF10 (CAS number 83016-70-0), Jeffcat DMEA (CAS number 108-01-0) and Dabco T (CAS number 2212-32-0). Reaction catalysts of this type have the effect of reducing the VOC value.

[0069] The amount of the catalyst (g) is preferably 0.1 to 5 mass %, particularly preferably 0.1 to 3.5 mass %, based on the total mass of the resins.

[0070] Additives and / or auxiliaries (h) Additives and / or auxiliaries (h) that may be used include, but are not limited to, surfactants, preservatives, colorants, antioxidants, reinforcing agents, stabilizers, and water absorbers. In the production of polyurethane foams, it is generally highly preferred to use small amounts of surfactants to stabilize the foaming reaction mixture until curing. Such surfactants advantageously include liquid or solid organosilicone surfactants used in sufficient amounts to stabilize the foaming reaction mixture. Typically, the amount of auxiliaries, especially surfactants, is preferably 0 to 15% by weight, more preferably 0.5 to 6% by weight, based on the total weight of the resin.

[0071] Further information on the use and action of said auxiliaries and additives, as well as further examples, can be found, for example, in “Kunststoffhandbuch, Band 7, Polyurethane” [“Plastics handbook, volume 7, Polyurethanes”], Carl Hanser Verlag, 3rd edition 1993, chapter 3.4.

[0072] The mass ratio of the polyol component to the isocyanate component is in the range of 1:0.6 to 1:2, preferably 1:0.7 to 1:1.

[0073] Manufacturing method of PU composite material In a further aspect, the present invention relates to a method for producing said PU composite material, said method comprising the steps of: 1) providing reinforcing fibers in the form of a continuous phase; 2) preparing a polyol component by mixing the following materials in a tank at a temperature of 20-80°C: (b) at least one polyol that is reactive towards isocyanates; (c) optionally a chain extender and / or a crosslinker; (d) flame retardants; (e) optionally a filler; (f) foaming agents; (g) Catalysts; and (h) optionally additives and / or auxiliaries; 3) mixing the polyol component obtained in step 2) with the isocyanate component and optionally reinforcing fibers in the form of a discontinuous phase at a temperature of 20-80° C. to obtain a mixture; 4) spraying or extruding the mixture obtained in step 3) by means of a first nozzle or extrusion head onto the reinforcing fibers in the form of a continuous phase provided in step 1) and, optionally, spraying the reinforcing fibers in the form of a discontinuous phase by means of a second nozzle onto the reinforcing fibers in the form of a continuous phase provided in step 1) to obtain a sprayed or extruded product; 5) hot pressing the sprayed or injected product obtained in step 4) in a mold having a temperature of 40-180°C under a hot press clamping force of 100-2000 tons; and 6) demolding and optional trimming; Including, The polyurethane composite material obtained in step 6) contains 35 to 75% by mass of reinforcing fibers and 25 to 65% by mass of polyurethane foam, based on the total mass of the polyurethane composite material; The reinforcing fibers include 75 to 100 mass % of reinforcing fibers in the form of a continuous phase and 0 to 25 mass % of reinforcing fibers in the form of a discontinuous phase, based on the total mass of the reinforcing fibers; The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers.

[0074] In one embodiment, the total amount of reinforcing fibers in the form of a continuous phase and optionally in the form of a discontinuous phase used in steps 1), 3) and 4), and the total amount of the polyol component and the isocyanate component used in step 3) is about (35-75):(25-65) in mass ratio.

[0075] In one embodiment, the reinforcing fibers in the form of a discontinuous phase in step 3) are obtained by cutting long fibers in situ and added in a certain proportion to the mixture of the isocyanate component and the polyol component of the polyurethane, and the length of the cut reinforcing fibers is 6-100 mm, preferably 8-80 mm, more preferably 10-50 mm, and even more preferably 12-25 mm.

[0076] In one embodiment, the reinforcing fibers in the form of a continuous phase in step 1) are in the form of a mat, a woven fabric, or a combination thereof.

[0077] Spray Transfer Molding (STM) Process In one embodiment, the present invention provides a spray transfer molding (STM) process for producing said PU composite material, comprising: 1) providing reinforcing fibers in the form of a continuous phase; 2) preparing a polyol component by mixing the following materials in a tank at a temperature of 20-80°C: (b) at least one polyol that is reactive towards isocyanates; (c) optionally a chain extender and / or a crosslinker; (d) flame retardants; (e) optionally a filler; (f) foaming agents; (g) Catalysts; and (h) optionally additives and / or auxiliaries; 3) mixing the polyol component obtained in step 2) with an isocyanate component at a temperature of 20 to 80°C to obtain a mixture; 4) spraying the mixture obtained in step 3) by means of a first nozzle onto the reinforcing fibers in the form of a continuous phase provided in step 1) and, optionally, spraying the reinforcing fibers in the form of a discontinuous phase by means of a second nozzle onto the reinforcing fibers in the form of a continuous phase provided in step 1) to obtain an atomized product; 5) hot pressing the sprayed product obtained in step 4) in a mold having a temperature of 40-180°C under a hot press clamping force of 100-2000 tons; and 6) demolding and optional trimming; providing a process including wherein the polyurethane composite material obtained in step 6) contains 35 to 75 mass % of reinforcing fiber and 25 to 65 mass % of polyurethane foam based on the total mass of the polyurethane composite material; The reinforcing fibers include 75 to 100 mass % of reinforcing fibers in the form of a continuous phase and 0 to 25 mass % of reinforcing fibers in the form of a discontinuous phase, based on the total mass of the reinforcing fibers; The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers.

[0078] In one embodiment, the process comprises in step 1) providing 1 to 4 layers, such as 1, 2, 3 or 4 layers, of reinforcing fibers in a continuous phase.

[0079] In one embodiment, in step 1), the open mold is preheated to a temperature of 40 to 180°C, preferably 70 to 150°C, more preferably 90 to 130°C.

[0080] In one embodiment, in step 4), the mixture obtained in step 3) is sprayed onto the reinforcing fiber layer using a first nozzle. In one embodiment, in step 4), the first nozzle moves at a speed such that the resulting PU composite material is relatively thin, for example, with a thickness of 0.5-10 mm, preferably 1-5 mm, more preferably 1-3 mm, and even more preferably 1-2 mm.

[0081] In one embodiment, in step 4), spraying of the mixture is carried out with a first nozzle that moves continuously from one end to the other end on the two surfaces of the reinforcing fiber layer. In this embodiment, spraying may be carried out on the first surface of the reinforcing fiber layer, and then the PU with the reinforcing fiber layer is picked up, turned over, placed continuously, and spraying is carried out on the second surface of the reinforcing fiber layer.

[0082] In another embodiment, in step 4), spraying of the mixture is carried out onto one surface of the reinforcing fiber layer.

[0083] In a preferred embodiment, the process includes in step 4) spraying reinforcing fibers in the form of a discontinuous phase onto the reinforcing fiber layer using a second nozzle. In this embodiment, the spraying of the reinforcing fibers in the form of a discontinuous phase may be carried out over the entire area or over a partial area of ​​the composite material in question, as desired. In this embodiment, the discontinuous reinforcing fibers are sprayed simultaneously with the spraying of the mixture obtained in step 3). Thus, the discontinuous reinforcing fibers can be arranged and dispersed in the mixture obtained in step 3).

[0084] In one embodiment, the total amount of reinforcing fibers in the form of a continuous phase and optionally in the form of a discontinuous phase used in steps 1) and 4) and the total amount of the polyol component and the isocyanate component used in step 3) is about (35-75):(25-65) in mass ratio.

[0085] In certain embodiments, the reinforcing fibers comprise 100% by weight of the reinforcing fibers in the form of a continuous phase, based on the total weight of the reinforcing fibers.

[0086] In one embodiment, in step 5), the mold is closed and held for 1 to 15 minutes, preferably 90 seconds to 10 minutes, more preferably 2 to 8 minutes.

[0087] In one embodiment, in step 5), the mold is closed and maintained at a temperature of 40 to 180° C., preferably 70 to 150° C., and more preferably 90 to 130° C. In one embodiment, in step 5), the mold is closed and maintained under a hot press clamping force of 100 to 2000 tons, preferably 200 to 1500 tons, and more preferably 300 to 1000 tons.

[0088] In one embodiment, the PU composite may be optionally manufactured to include at least one insert, such as a metal sheet, metal foil, or solid flame retardant layer. In one embodiment, a coated article is obtained that includes the PU composite and at least one metal sheet. In another embodiment, a coated article is obtained that includes the PU composite and a layer of solid flame retardant.

[0089] In one embodiment, in step 6), the trimming step is performed simultaneously with demolding, using a knife designed on the mold for trimming cut in the STM process. In this embodiment, the device used in this STM process is designed with a knife on the mold for trimming cut.

[0090] Long Fiber Injection (LFI) Process In another aspect, the present invention provides a method for producing 1) providing reinforcing fibers in the form of a continuous phase; 2) The following materials: (b) at least one polyol that is reactive towards isocyanates; (c) optionally a chain extender and / or a crosslinker; (d) flame retardants; (e) optionally a filler; (f) foaming agents; (g) Catalysts; and (h) optionally additives and / or auxiliaries in a tank at a temperature of 20 to 80° C. to prepare a polyol component; 3) mixing the polyol component obtained in step 2) with an isocyanate component and a discontinuous phase of reinforcing fibers at a temperature of 20 to 80°C to obtain a mixture; 4) injecting the mixture obtained in step 3) by means of an injection head onto the reinforcing fibers in the form of a continuous phase provided in step 1) to obtain an extruded product; 5) hot pressing the injection molded article obtained in step 4) in a mold at a temperature of 40 to 180° C. with a hot press clamping force of 100 to 2000 tons; 6) Demolding and optional trimming step The present invention further provides a long fiber injection (LFI) process for producing the PU composite material, comprising: wherein the polyurethane composite material obtained in step 6) comprises 35-75% by mass of reinforcing fibers and 25-65% by mass of polyurethane foam based on the total mass of the polyurethane composite material; The reinforcing fibers include 75-100% by mass of reinforcing fibers in the form of a continuous phase and >0-25% by mass of reinforcing fibers in the form of a discontinuous phase, based on the total mass of the reinforcing fibers; The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers.

[0091] In one embodiment, the process comprises in step 1) providing 1 to 4 layers, such as 1, 2, 3 or 4 layers, of reinforcing fibers in a continuous phase.

[0092] In one embodiment, in step 1), the open mold is preheated to a temperature of 40 to 180°C, preferably 70 to 150°C, more preferably 90 to 130°C.

[0093] In one embodiment, in step 3), the mixing is carried out in a mixing chamber immediately prior to injection.

[0094] In one embodiment, in step 3), the reinforcing fibers in the form of a discontinuous phase are obtained by chopping long fibers on-site just prior to the mixing chamber and are added at a constant rate to the mixture of isocyanate and polyol components (i.e., to the mixing chamber). In this embodiment, the reinforcing fibers before chopping are in the form of fiber coils and wound on bobbins.

[0095] In one embodiment, the reinforcing fibers are added in a proportion such that the resulting PU composition has a fiber content of 35-75% by weight of the reinforcing fibers relative to the total weight of the PU composite.

[0096] In one embodiment, the total amount of reinforcing fibers in the form of a continuous phase and reinforcing fibers in the form of a discontinuous phase used in steps 1) and 3) and the total amount of polyol component and isocyanate component used in step 3) are in a mass ratio of about (35-75):(25-65).

[0097] In one embodiment, in step 3), the reinforcing fibers in the form of a discontinuous phase have a size of 6 to 100 mm, preferably 8 to 80 mm, more preferably 10 to 50 mm, and even more preferably 12 to 25 mm.

[0098] In one embodiment, in step 4), an injection head is used to inject the mixture obtained in step 3) onto the surface of the reinforcing fiber layer in the open mold.

[0099] In one embodiment, in step 5), the mold is closed and maintained at a temperature of 40 to 180°C, preferably 70 to 150°C, more preferably 90 to 130°C. In one embodiment, in step 5), the mold is closed and maintained under a hot press clamping force of 100 to 2000 tons, preferably 200 to 1500 tons, more preferably 300 to 1000 tons. In one embodiment, in step 5), the mold is closed and maintained for 1 to 15 minutes, preferably 90 seconds to 10 minutes, more preferably 2 to 8 minutes.

[0100] In one embodiment, the PU composite may be optionally manufactured to include at least one insert, such as a metal sheet, metal foil, or solid flame retardant layer. In one embodiment, a coated article is obtained that includes the PU composite and at least one metal sheet. In another embodiment, a coated article is obtained that includes the PU composite and at least one metal foil.

[0101] In one embodiment, in step 6), the trimming step is performed simultaneously with demolding using a knife designed on the mold for trimming cuts in the LFI process. In this embodiment, the equipment used in this LFI process is designed with a knife on the mold for trimming cuts.

[0102] Surprisingly, the inventors have found that all the above processes result in a thickness of 0.5-10 mm, preferably 1-5 mm, more preferably 1-3 mm, even more preferably 1-2 mm, and a reduced density, e.g. 1.8 g / mm 3 Less than 1.6g / mm 3 less than 1.5g / mm 3 less than 1.3 g / mm 3 Less than 1.2 g / mm 3 It has been found that it is possible to produce PU composites having a density less than 1000 MPa. Furthermore, they have the advantages of low raw material requirements, good impregnation between the fiber and the PU, low cost, short cycle time, etc.

[0103] Additionally, the relatively low pressure and temperature requirements for STM and LFI processes lead to reduced tooling costs. Moreover, STM and LFI can successfully fabricate complex parts with high resolution features, including thick and thin walls.

[0104] Coated Articles In one aspect, the present invention provides a coated article comprising at least one of said polyurethane composites or a polyurethane composite obtained by said process.

[0105] In one embodiment, the coated article has a thickness of 1 to 5 mm, preferably 1.2 to 3 mm.

[0106] In one embodiment, the coated article further comprises at least one metal sheet disposed on at least one side of the at least one PU composite sheet. In a preferred embodiment, the coated article comprises two metal sheets disposed on both sides of the PU composite sheet. In this embodiment, the coated article comprises a PU composite sheet as a core layer and two metal sheets disposed on both sides of the core layer to form a sandwich-like structure. In another preferred embodiment, the coated article comprises one metal sheet disposed on one side of the PU composite sheet. In some alternative embodiments, the coated article comprises one metal sheet and two PU composite sheets disposed on both sides of the metal sheet. In one embodiment, the metal sheets are independently selected from aluminum alloy, iron, steel, and aluminum sheets.

[0107] The metal sheet may have a thickness of 0.08 to 1.2 mm, preferably 0.08 to 0.6 mm, more preferably 0.12 to 0.4 mm, and most preferably 0.2 to 0.3 mm.

[0108] In a preferred embodiment, the metal sheet has a thickness of 0.2 to 1.2 mm, preferably 0.5 to 1.0 mm. It has been found that metal sheets of such thickness advantageously provide improved mechanical strength, making it possible to cover articles with such metal sheets and still meet mechanical strength requirements.

[0109] The coated article of the present invention can be used as a top cover for a battery pack.

[0110] The coated article according to the present invention has good fire protection performance, electromagnetic interference (EMI) shielding performance, excellent electrical insulation and voltage resistance, and is suitable for use as the upper cover of a battery pack. In addition, the coated article according to the present invention passes the UL94 V0 grade at a thickness of 2 mm. A battery pack including the coated article according to the present invention as the upper cover passes the external fire burning test according to GB 38031-2020.

[0111] The coated article according to the present invention further has a good shielding efficiency (SE). In one embodiment, the coated article exhibits a shielding factor (dB) of at least 40, preferably at least 50, more preferably at least 60. The dB value is calculated by the formula [dB]=20×log(E0 / E1), where E0 is the electric field strength without the coating and E1 is the electric field strength with the coating. For example, a dB value of 60 indicates that the coated article reflects and / or absorbs 99.9% of the electromagnetic energy.

[0112] II. Laminated Products In one aspect, the present invention relates to a laminate product comprising at least one insulation layer and at least two PU composite layers disposed on either side of the insulation layer, where the insulation layer comprises a binder and an insulation material dispersed in the binder.

[0113] As shown in FIG. 4, the laminated product includes two PU composite layers and one insulation layer disposed between the two PU composite layers.

[0114] The PU composite material contained in the laminate product has the same meaning as described in the "PU composite material" section or in the "PU composite material manufacturing method" section (see paragraph I. PU composite material), unless otherwise specified, and will not be repeated here for the sake of brevity.

[0115] In one embodiment, the insulation layer comprises 10% to 70% by weight, preferably 20% to 50% by weight, more preferably 20% to 40% by weight of insulation material, based on the total weight of the insulation layer. Alternatively, the insulation layer comprises 50 to 500 g / m 2 , 50~200g / m 2 , 100~200g / m 2 Surface density is understood to refer to the mass (g) of material per square meter. If the mass percent / area density of the insulating material is too high, it will be difficult for the insulating material to bond to form a film, whereas if the mass percent / area density of the insulating material is too low, the corresponding insulating properties will not be achieved.

[0116] In one embodiment, the insulation layer is an intumescent insulation layer and the insulation material is an intumescent insulation material.

[0117] When exposed to high temperatures, the intumescent insulation releases non-combustible gases (SO2, CO2, ammonia, etc.) and / or water vapor, expanding to form a carbon foam layer. The released non-combustible gases and / or water vapor dilute the surrounding oxygen concentration, reducing the risk of fire. Furthermore, the formed carbon foam layer has good insulation performance due to its loose structure, preventing high temperatures from spreading to the surroundings, thereby acting as a good thermal barrier.

[0118] Suitable intumescent insulating materials include, but are not limited to, phosphorus-containing materials, nitride-containing materials, sulfur-containing materials, boron-containing materials, compounds that release water vapor (e.g., calcium hydroxide, magnesium hydroxide, aluminum hydroxide, expandable graphite (EG)), pentaerythritol, kaolin, or combinations thereof.

[0119] For example, phosphorus-containing materials include phosphates such as sodium, potassium, or ammonium phosphate, ammonium polyphosphate (APP), monoammonium phosphate, diammonium phosphate, trichloroethyl phosphate (TCEP), trichloropropyl phosphate (TCPP), ammonium pyrophosphate, triphenyl phosphate, etc. Nitrogen-containing materials include melamine, melamine salts, salts of phosphoric acid, guanidine, melamine cyanurate, melamine formaldehyde, methylolated melamine, hexamethoxymethylmelamine, urea, dimethylurea, melamine pyrophosphate, dicyandiamide, guanylurea phosphate, and glycine. Sulfur-containing materials include sulfonates such as sodium, potassium, or ammonium sulfonates, paratoluenesulfonates, sulfates such as sodium sulfate, potassium sulfate, or ammonium sulfate. Boron-containing materials include boric acid and borates such as ammonium pentaborate, zinc borate, sodium borate, lithium borate, aluminum borate, magnesium borate, and borosilicates. Compounds that decompose upon exposure to heat to release water vapor include, but are not limited to, calcium hydroxide, magnesium dihydroxide, aluminum trihydroxide, or expandable graphite (EG). Other suitable intumescent insulating materials include polyfunctional alcohols such as pentaerythritol, kaolin, and the like.

[0120] In one embodiment, the expandable graphite has an average particle size of 50 μm to 500 μm, preferably 50 μm to 300 μm, more preferably 100 μm to 200 μm. The inventors have found that a particle size of more than 500 μm makes processing difficult. On the other hand, if the particle size is less than 50 μm, the expansion rate is limited, which impairs the heat insulating performance.

[0121] In one embodiment, the binder is selected from polyurethane, epoxy resin, polyethylene, polypropylene, polystyrene, or combinations thereof.

[0122] In a preferred embodiment, the binder is a polyurethane. As described in paragraph I (PU composite), polyurethane is a reaction product of a reaction mixture containing an isocyanate and a polyol reactive with the isocyanate. The isocyanate and the polyol reactive with the isocyanate are the same as the "isocyanate component" and "polyol reactive with the isocyanate" described in paragraph I (PU composite). For the sake of brevity, they will not be repeated here.

[0123] In one embodiment, the preferred polyol has a weight average molecular weight of 1000 to 10000, preferably 4000 to 6000. Preferably, the polyol has a functionality of 2 to 3. The inventors have found that laminated products made using the polyurethane materials defined above are elastic and non-rigid.

[0124] In one embodiment, the laminated product has an expansion ratio of 5 to 20. In other words, the laminated product can swell and expand to a product that is 5 to 20 times thicker than the original product. Preferably, the laminated product has a thickness of less than 5 mm before expansion and a maximum thickness of less than 25 mm after expansion. This characteristic is particularly advantageous when the laminated product is used as a shell for a battery system. Since the internal cavity space of the battery system is generally limited, it is expected that the foamed laminated product will not be too thick. Thus, with the preferred mass percentage and areal density of the insulating material, the thickness of the laminated product after expansion will be 25 mm or less, which will not destroy the battery components contained within the battery system.

[0125] The expansion ratio is defined as the expanded thickness of the laminated product divided by the thickness before expansion.

[0126] In one embodiment, the laminate product further comprises at least one substrate layer disposed between the insulation layer and the polyurethane composite layer, substrate layers include fabric sheets, plastic sheets, and metal sheets.

[0127] The textile sheets are made, for example, from fiberglass (GF), carbon fibers, natural fibers (e.g. bamboo fibers), especially natural fibers in the form of woven or non-woven fabrics, the metal sheets are made, for example, from aluminum alloys, iron, steel or aluminum, and the plastic sheets are made, for example, from polyethylene (PE), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene (PP), polyurethane (PU), polyamide (PA), polyvinyl butyral (PVB) or ethylene vinyl acetate (EVA).

[0128] In one embodiment, the laminated product further includes at least one metal sheet disposed on a side of the laminated product. When the laminated product is applied to a battery pack, the metal sheet is disposed on the side opposite the battery cell. The metal sheet mainly serves to further improve the mechanical strength of the laminated product.

[0129] A method for making the thermal insulation layer is shown in Figure 5. Specifically, in some embodiments, the thermal insulation layer is made of: i) mixing an insulating material with a binder; ii) applying the mixture obtained in step i) onto the surface of a substrate (e.g., by spraying or knife coating) and allowing the mixture to harden; and iii) Optionally removing the substrate to obtain a thermal barrier layer. Manufactured by.

[0130] In certain embodiments in which the binder is a polyurethane, the insulating layer comprises: i) mixing an insulating material with a polyol component; ii) mixing the mixture obtained in step i) with an isocyanate component; iii) applying the mixture obtained in step ii) onto the surface of a substrate (e.g., by spraying or knife coating) and allowing the mixture to harden; and iv) Optionally removing the substrate to obtain a thermal barrier layer. Manufactured by.

[0131] The substrate used in the above-mentioned manufacturing method includes a release paper, a fiber sheet, a plastic sheet, a metal sheet, etc. When the substrate is a release paper, the release paper is removed from the final heat insulating layer.

[0132] In one embodiment, the laminated product passes the UL94 V0 grade for fire resistance testing. In one embodiment, the laminated product passes the UL94 5VA fire resistance testing.

[0133] In one embodiment, the laminated product is fire tested on one side at 800-1300°C (called T1) for 10 minutes. The results show that the temperature on the other side (called T2) is below 400°C. In a preferred embodiment, T2 is below 350°C. In a more preferred embodiment, T2 is below 300°C. In an even more preferred embodiment, T2 is below 280°C. In a most preferred embodiment, T2 is below 260°C.

[0134] Manufacturing method of laminated products In a further aspect, the present invention provides a method for producing a method for treating a cancer cell comprising the steps of: 1) i) Mix the insulation material and binder; ii) applying the mixture of step i) to the surface of the substrate (e.g., by spraying or knife coating) and allowing the mixture to cure; iii) Optionally removing the substrate providing a heat insulating layer by 2) providing reinforcing fibers in the form of a continuous phase arranged on both sides of the insulation layer obtained in step 1); 3) The following materials: (b) at least one polyol that is reactive towards isocyanates; (c) optionally a chain extender and / or a crosslinker; (d) flame retardants; (e) optionally a filler; (f) foaming agents; (g) Catalysts; and (h) optionally additives and / or auxiliaries in a tank at a temperature of 20 to 80° C. to prepare a polyol component; 4) mixing the polyol component obtained in step 3) with an isocyanate component and optionally reinforcing fibers in the form of a discontinuous phase at a temperature of 20-80° C. to obtain a mixture; 5) spraying or extruding the mixture obtained in step 4) by means of a first nozzle or extrusion head onto the reinforcing fibers in the form of a continuous phase arranged on both sides of the insulation layer provided in step 2), and optionally spraying reinforcing fibers in the form of a discontinuous phase by means of a second nozzle onto the reinforcing fibers in the form of a continuous phase provided in step 2) to obtain a sprayed or extruded product; 6) hot pressing the sprayed or injected product obtained in step 5) in a mold having a temperature of 40-180°C under a hot press clamping force of 100-2000 tons; and 7) Demolding and optional trimming, thereby obtaining a laminated product comprising a polyurethane composite material disposed on both sides of the insulating layer. a method for producing the laminated product, comprising: Here, the polyurethane composite material contains 35 to 75 mass% of reinforcing fiber and 25 to 65 mass% of polyurethane foam based on the total mass of the polyurethane composite material, The reinforcing fibers comprise 75-100% by mass of reinforcing fibers in the form of a continuous phase and 0-25% by mass of reinforcing fibers in the form of a discontinuous phase, based on the total mass of the reinforcing fibers; and The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers.

[0135] For the purpose of easy understanding, FIG. 6 shows an example of a method for manufacturing a laminated product.

[0136] In one embodiment, the reinforcing fibers in the form of a discontinuous phase in step 4) are obtained by cutting long fibers in situ and added in a certain ratio to the mixture of the isocyanate component and the polyol component of the polyurethane, and the length of the cut reinforcing fibers is 6-100 mm.

[0137] In one embodiment, the reinforcing fibers in the form of a continuous phase in step 1) are in the form of a mat, a woven fabric, or a combination thereof.

[0138] It should be noted that suitable materials for making the insulating layer are the same as those described in paragraph II (Laminated Product). Suitable materials used in steps 2) to 5) above are the same as those described in paragraph I (PU Composite Material) and will not be repeated here for the sake of brevity.

[0139] Spray Transfer Molding (STM) Process for the Manufacturing of Laminated Products In one aspect, the present invention provides 1) i) Mix the insulation material and binder; ii) applying the mixture of step i) to the surface of the substrate (e.g., by spraying or knife coating) and allowing the mixture to cure; iii) Optionally remove the substrate providing a heat insulating layer by 2) providing reinforcing fibers in the form of a continuous phase arranged on both sides of the insulation layer obtained in step 1); 3) The following materials: (b) at least one polyol that is reactive towards isocyanates; (c) optionally a chain extender and / or a crosslinker; (d) flame retardants; (e) optionally a filler; (f) foaming agents; (g) Catalysts; and (h) optionally additives and / or auxiliaries in a tank at a temperature of 20 to 80° C. to prepare a polyol component; 4) mixing the polyol component obtained in step 3) with an isocyanate component at a temperature of 20 to 80°C to obtain a mixture; 5) spraying the mixture obtained in step 4) by means of a first nozzle onto the reinforcing fibers in the form of a continuous phase arranged on both sides of the insulation layer provided in step 2), and optionally spraying the reinforcing fibers in the form of a discontinuous phase by means of a second nozzle onto the reinforcing fibers in the form of a continuous phase provided in step 2) to obtain a sprayed product; 6) hot pressing the sprayed product obtained in step 5) in a mold having a temperature of 40-180°C under a hot press clamping force of 100-2000 tons; and 7) Demolding and optionally trimming, thereby obtaining a laminated product comprising a polyurethane composite material disposed on both sides of the insulating layer. A spray transfer molding (STM) process for producing said laminated product, comprising: Here, the polyurethane composite material contains 35 to 75 mass% of reinforcing fiber and 25 to 65 mass% of polyurethane foam based on the total mass of the polyurethane composite material, The reinforcing fibers comprise 75-100% by mass of reinforcing fibers in the form of a continuous phase and 0-25% by mass of reinforcing fibers in the form of a discontinuous phase, based on the total mass of the reinforcing fibers; and The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers.

[0140] It should be noted that all elements (e.g., without limitation, raw materials used, conditions (temperature, pressure, etc.), equipment or devices, order of steps) used in the "Spray Transfer Molding (STM) process for manufacturing PU composites" also apply to steps 2)-7) of the STM process for manufacturing laminated products, unless otherwise specified, and will not be repeated here for the sake of brevity.

[0141] Long Fiber Injection(LFI) Process for the Manufacturing of Laminated Products. In another aspect, the present invention provides a method for producing 1) i) Mix the insulation material and binder; ii) applying the mixture of step i) to the surface of the substrate (e.g., by spraying or knife coating) and allowing the mixture to cure; iii) Optionally removing the substrate providing a heat insulating layer by 2) providing reinforcing fibers in the form of a continuous phase arranged on both sides of the insulation layer obtained in step 1); 3) The following materials: (b) at least one polyol that is reactive towards isocyanates; (c) optionally a chain extender and / or a crosslinker; (d) flame retardants; (e) optionally a filler; (f) foaming agents; (g) Catalysts; and (h) optionally additives and / or auxiliaries in a tank at a temperature of 20 to 80° C. to prepare a polyol component; 4) mixing the polyol component obtained in step 3) with the isocyanate component and the reinforcing fibers in the form of a discontinuous phase at a temperature of 20-80°C to obtain a mixture; 5) injecting the mixture obtained in step 4) by means of an injection head onto the reinforcing fibers in the form of a continuous phase arranged on both sides of the insulation layer provided in step 2) to obtain an injected product; 6) hot pressing the injected product obtained in step 5) in a mold having a temperature of 40-180°C under a hot press clamping force of 100-2000 tons; and 7) Demolding and optional trimming, thereby obtaining a laminated product comprising a polyurethane composite material disposed on both sides of the insulating layer. A long fiber injection (LFI) process for the manufacture of laminated products, comprising: Here, the polyurethane composite material contains 35 to 75 mass% of reinforcing fiber and 25 to 65 mass% of polyurethane foam based on the total mass of the polyurethane composite material, The reinforcing fibers comprise 75-100% by mass of reinforcing fibers in the form of a continuous phase and 0-25% by mass of reinforcing fibers in the form of a discontinuous phase, based on the total mass of the reinforcing fibers; and The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers.

[0142] It should be noted that all elements (e.g., without limitation, raw materials used, conditions (temperature, pressure, etc.), equipment or devices, order of steps) used in the "Long Fiber Injection (LFI) Process for Producing PU Composites" also apply to steps 2)-7) of the LFI process for producing laminated products, unless otherwise specified, and will not be repeated here for the sake of brevity.

[0143] Surprisingly, it has been found in the present application that said laminated product, or a laminated product produced by said method, exhibits low weight, good mechanical strength, flame retardancy and at the same time good thermal insulation properties. Moreover, said method is carried out in a robust and simple manner. Likewise, said laminated product is obtained cost-effectively.

[0144] In yet another aspect, the present invention relates to a coated article suitable for a battery system, comprising at least one of the laminate products described above, or a laminate product produced by the method described above.

[0145] It should be noted that throughout this application, materials referred to in process embodiments have the same meaning as in product embodiments, and the general, preferred, more preferred, and most preferred definitions and amounts of materials set forth in the product section also apply to the methods of making the products and articles made from the products, unless otherwise specified.

[0146] Working Example The present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto.

[0147] General Description The following starting materials are used in the examples: [ka] [ka]

[0148] The following methods were used to determine the properties: kg / m 3 Density at GB / T 6343-2008 Flame retardant: UL94 V0 UL 94 5VA standard Tensile strength / modulus GB / T1447-2005 Flexural strength / modulus GB / T1449-2005.

[0149] Example A: PU Composite I. Manufacturing example The PU composite materials of Examples 1-5 and Comparative Example 1 were prepared using the amounts of polyol component, isocyanate component and reinforcing fiber specified in Table 1. The PU composite material of Comparative Example 2 was purchased commercially under the name HY3102SMC from HUAYUAN ADV. MATERIALS, which was prepared by the prior art sheet molding compound (SMC) process.

[0150] [Table 1-1] [Table 1-2] *As stated in the preceding paragraph, the fillers contained in the polyol component do not include reinforcing fibers.

[0151] Examples 1 to 3 The PU composite material according to the present invention was produced by a long fiber injection (LFI) process, which includes the following steps:

[0152] The materials of polyol component A listed in Table 1 were mixed to form polyol component A. The materials of isocyanate component B listed in Table 1 were mixed to form isocyanate component B. The resulting polyol component A and isocyanate component B were statically mixed at a pressure of 4 bar to obtain a mixture having a viscosity of about 200 mPa·s, and reinforcing fibers were chopped and added to the resulting mixture with stirring to obtain the final mixture. The length of the chopped reinforcing fibers was 15 mm. The final mixture was preheated to about 110 °C and was poured into an open mold equipped with knives for cutting trimming and drilling screw holes, into which an insert (e.g., glass fiber mat, and / or metal sheet, metal foil, solid flame retardant layer) can be fixed, into which two layers of glass fiber mat are placed, at a thickness of about 650 g / m. 2 The mold was then closed and clamped at approximately 800 tons.

[0153] The part was molded for 5 minutes and demolded, resulting in a product with a thickness of approximately 1.8 mm.

[0154] From Table 1, it can be seen that the amounts of continuous and discontinuous reinforcing fibers used and the amounts of polyol component A and isocyanate component B used as starting materials were in a ratio of (35-55):(45-65).

[0155] Examples 4 and 5 The PU composite material according to the present invention was produced by a spray transfer molding (STM) process, which includes the following steps:

[0156] The materials for polyol component A listed in Table 1 were mixed and maintained at a tank temperature of 30°C to 40°C to prepare polyol component A with reduced viscosity. The materials for isocyanate component B listed in Table 1 were mixed to form isocyanate component B. Polyol component A and isocyanate component B were impingement mixed at a pressure of about 150 bar to obtain a mixture with a viscosity of about 500 mPa s. This mixture was then applied to the surface of two layers of glass fiber mats at a viscosity of about 650 g / m2. 2 was sprayed in an amount of

[0157] At approximately atmospheric pressure, the resulting glass fiber filled PU is placed by the robot onto an open mold, preheated to about 110°C and equipped with knives for cutting trimming and drilling screw holes, into which an insert (e.g., glass fiber mat, and / or metal sheet, metal foil, solid flame retardant layer) can be fixed, after which the mold is closed and clamped with about 500 tons.

[0158] The parts were molded for 5 minutes and then demolded, yielding products with thicknesses of approximately 1.8 mm to 2.4 mm.

[0159] Comparative Example 1 PU composite materials were prepared by the same process as described in Examples 1 to 3. A product with a thickness of about 1.4 mm was obtained.

[0160] II. Effects of the embodiment Property testing of PU composite products The physical and chemical properties of the PU composite products of the manufacturing examples are shown in Table 2.

[0161] [Table 2]

[0162] Examples 6-7 - Testing the electromagnetic shielding properties of coated articles Coated articles of Examples 6 and 7 were prepared containing the PU composites of Examples 2 and 4, respectively. The coated articles included a sheet of the PU composite as a core layer and an aluminum alloy sheet having a thickness of 0.2 mm disposed on one side of the core layer.

[0163] The electromagnetic wave shielding performance of these coated articles was tested and the results are listed in Table 3.

[0164] [Table 3]

[0165] Examples 8-10 - Testing the fire resistance of battery packs Battery packs of Examples 8 to 10 were prepared, each including a coated article of Examples 3 to 5. Each battery pack included a coated article and a bottom tray. The bottom tray was made by punching an aluminum alloy sheet.

[0166] The fire resistance performance of these battery packs was tested and the results are listed in Table 4.

[0167] External fire test: GB 38031-2020 Test method: (8.2.7.1) Ignite a fuel pan from a distance of 3m or more from the target Preheat the fire for 60 seconds - Move the fuel pan under the battery pack - Expose the battery pack directly to fire for 70 seconds Add a cover to the fuel pan and continue the test for 60 seconds. Remove the fuel pan Observe the battery pack for 2 hours Requirements: (5.2.7) The battery pack must not explode. *Nickel metal hydride batteries are not applicable.

[0168] [Table 4]

[0169] As can be seen from Table 3, the coated articles comprising the PU composite material according to the invention have good EMI shielding performance.

[0170] As can be seen from Table 4, the battery pack including the coated article according to the present invention as a top cover passes the external fire burn test.

[0171] Examples 11 to 13 Voltage resistance test The coated article of Example 11 includes two layers of the PU composite of Example 4 hot pressed together. The coated article of Example 12 includes one PU composite of Example 4 and one steel plate (thickness=0.2 mm) disposed on one side of the PU composite. The coated article of Example 13 includes one steel plate (thickness=0.2 mm) and two layers of the PU composite of Example 4 disposed on both sides of an aluminum alloy plate.

[0172] To evaluate their voltage resistance performance, the cover articles of Examples 11-13 were tested against high DC voltage (3000V) for 60 seconds. Then, the coated articles were burned at 1000°C for 30 minutes. For the coated article of Example 12, the PU composite side was burned with fire. Then, the burned coated articles of Examples 11-13 were again tested against high DC voltage (3000V or 1000V) for 60 seconds.

[0173] The results are shown in Table 5 below. It should be noted that the coated articles of Examples 11-13 before combustion exhibited a leakage current of less than 3 mA under a voltage of 3000 V. The coated article of Example 12 after combustion exhibited a leakage current of less than 3 mA under a voltage of 1000 V, while the coated articles of Examples 11 and 13 also exhibited a leakage current of less than 3 mA under a voltage of 3000 V. Additionally, the coated articles of Examples 11-13 did not exhibit any dielectric breakdown or flashover.

[0174] These test results show that the coated articles of Examples 11 to 13 have excellent voltage resistance and electrical insulation properties, and are particularly suitable as covers / shells for battery systems.

[0175] [Table 5]

[0176] Example B: Laminated Product I. Manufacturing example Examples 14 to 17: Production of intumescent insulation layer The intumescent insulating layers of Examples 14 and 15 were prepared using the amounts of the polyol component, the isocyanate component and the intumescent component defined in Table 6.

[0177] [Table 6]

[0178] Example 14 An intumescent insulating layer according to the present invention was produced by a spray technique involving the following steps.

[0179] The materials for polyol component A' listed in Table 6 were mixed to form polyol component A'. The materials for isocyanate component B' listed in Table 6 were mixed to form isocyanate component B'. Expandable graphite was premixed with polyol component A' and kept in a tank at a temperature of 30°C to 40°C to obtain a premixed mixture. The premixed mixture and isocyanate component B' were mixed at a pressure of about 10 bar to obtain a mixture. The mixture was then cooled to about 100 g / m 2 The mixture was sprayed onto the release paper in an amount to provide an intumescent insulating layer (also referred to as an "IL100" layer) having an areal density of 1000 g / m2.

[0180] The release paper with the expandable heat insulating material was then heated in an oven at about 100° C. for 5 minutes to cure, after which the expandable heat insulating layer was peeled off from the release paper.

[0181] Example 15 The intumescent insulating layer according to the invention was produced by knife coating technique.

[0182] The materials for polyol component A' listed in Table 6 were mixed to form polyol component A'. The materials for isocyanate component B' listed in Table 6 were mixed to form isocyanate component B'. An expandable component including APP422, melamine, pentaerythritol, and kaolin was premixed with polyol component A' and kept in a tank at a temperature of 30°C to 40°C to obtain a premixed mixture. The premixed expandable mixture and isocyanate component B' were mixed at a pressure of about 150 bar to obtain a mixture. The mixture was then cooled to about 100 g / m 2 The mixture was knife coated onto the release paper in an amount to provide an intumescent insulating layer (also referred to as a layer of "IL100-2") having an areal density of 1000 g / g.

[0183] The release paper with the expandable heat insulating material was then heated in an oven at about 100° C. for 5 minutes to cure, after which the expandable heat insulating layer was peeled off from the release paper.

[0184] The intumescent insulation layers of Examples 16 and 17 were sprayed and knife coated at different rates to a thickness of about 150 g / m 2 and 230 g / m 2 The intumescent insulating layer was produced by the same process as described in Example 14, except that an intumescent insulating layer having an areal density of 1000 nm was obtained (also referred to as "IL150" or "IL230").

[0185] Examples 18 to 23: Preparation of laminated products The laminated article of Example 18 was produced by a spray transfer molding (STM) process that included the following steps.

[0186] As shown in FIG. 6, the intumescent insulation layer of Example 14 (ie, IL100) was provided with two layers of fiberglass mats placed on either side of the intumescent insulation layer.

[0187] The materials for polyol component A listed in Example 4 of Table 1 were mixed and maintained at a tank temperature of 30°C to 40°C to prepare polyol component A with reduced viscosity. The materials for isocyanate component B listed in Example 4 of Table 1 were mixed to form isocyanate component B. Polyol component A and isocyanate component B were impingement mixed at a pressure of about 150 bar to obtain a mixture having a viscosity of about 500 mPa s. This mixture was then applied to a glass fiber mat (areal density = 750 g / m) placed on one side of the intumescent insulation layer. 2 Approximately 650g / m 2 The mixture was sprayed onto a glass fiber mat (areal density = 200 g / m each) placed on the opposite side of the intumescent insulation layer. 2 Approximately 650g / m 2 was sprayed in an amount of

[0188] At approximately atmospheric pressure, the resulting product, including an intumescent insulation layer and two polyurethane composites arranged on either side of the intumescent insulation layer, was placed on an open mold, preheated to approximately 110°C by a robot, equipped with knives for cutting trimming and drilling screw holes, in which an insert (e.g., a glass fiber mat, and / or a metal sheet, metal foil, a solid flame retardant layer) can be fixed, and the mold was closed and clamped at approximately 500 tons.

[0189] The part was molded for 5 minutes and then demolded to yield a laminated product also called GF750 / IL100 / GF200.

[0190] The laminated products of Examples 19 and 20 were made by the same process as described in Example 18, except that Example 19 used the intumescent insulation layer of Example 16 (i.e., "IL150"), while Example 20 used the intumescent insulation layer of Example 17 (i.e., "IL230"). The laminated products of Examples 21 and 22 were made by the same process as described in Example 18, except that the areal density of the glass fiber mat was changed as shown in Table 7.

[0191] The laminated product of Example 23 was manufactured by the same process as Example 18, except that the intumescent insulation layer was made according to Example 15 (ie, IL100-2).

[0192] Comparative Example 3: A comparative example product was made by the same process as described in Example 18, except that no intumescent insulation layer was provided, and the product was designated GF750 / GF200.

[0193] II. Effects of the embodiment The laminated products produced according to Examples 18-23 and Comparative Example 3 are fire tested at 1300°C (T1) for 10 minutes on one side. The temperature on the opposite side is recorded as T2, as shown in Table 7.

[0194] [Table 7]

[0195] As shown in Table 7, the laminated products (Examples 18 to 23) produced according to the present invention exhibit excellent heat insulating performance, since the temperature of the opposite side T2 is less than 400° C. In particular, T2 of Examples 18 to 22 is even lower than 320° C.

[0196] To evaluate the voltage endurance performance of the laminated product, the laminated product of Example 22 was tested against a high DC voltage (3000V) for 60 seconds. The laminated product was then burned at 1000° C. for 30 minutes. The burned coated article of Example 22 was then again tested against a high DC voltage (3000V) for 60 seconds.

[0197] The results are shown in Table 8 below. It should be noted that the laminated product of Example 22 has a leakage current of less than 3 mA under a voltage of 3000 V before and after burning. In addition, no dielectric breakdown or flashover occurs.

[0198] These test results show that the laminated product of Example 22 has excellent voltage resistance and electrical insulation properties, and is particularly suitable as a cover / shell for a battery system.

[0199] [Table 8]

[0200] The structures, materials, components, compositions, and methods described herein are intended to be representative examples of the present invention, and it will be understood that the scope of the present invention is not limited by the scope of the examples. Those skilled in the art will recognize that the disclosed structures, materials, compositions, and methods can be modified to practice the present invention, and such modifications are considered to be within the scope of the present invention. Therefore, the present invention is intended to cover such modifications and variations that are within the scope of the appended claims and their equivalents.

Claims

1. A polyurethane composite material, wherein the polyurethane composite material contains 35 to 75% by mass of reinforcing fibers and 25 to 65% by mass of polyurethane foam based on the total mass of the polyurethane composite material, The polyurethane foam is as follows, (a) an isocyanate component comprising at least one isocyanate or isocyanate prepolymer and (b) at least one polyol reactive with the isocyanate, (c) optionally a chain extender and / or a crosslinking agent, (d) a flame retardant, (e) optionally a filler, (f) a blowing agent, (g) a catalyst, and (h) optionally additives and / or auxiliaries comprising a polyol component obtained from a two-component reaction system, The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers, and the reinforcing fibers contain 75 to 100% by mass of reinforcing fibers in the form of a continuous phase and 0 to 25% by mass of reinforcing fibers in the form of a discontinuous phase based on the total mass of the reinforcing fibers, A polyurethane composite material.

2. The polyurethane composite material according to claim 1, wherein the reinforcing fibers are impregnated with the polyurethane foam.

3. The polyurethane composite material according to claim 1 or 2, wherein the reinforcing fibers in the form of a continuous phase are in the form of a mat, a woven fabric, or a combination thereof.

4. The polyurethane composite material according to claim 3, wherein the polyurethane composite material contains 1 to 4 layers of mats, woven fabrics, or combinations thereof.

5. The polyurethane composite material according to claim 1 or 2, wherein the reinforcing fibers in the form of a discontinuous phase have a length of 6 to 100 mm.

6. The polyurethane composite material has a density of less than 2.2 g / cm 3 The polyurethane composite material according to claim 1 or 2, having a density of less than 2.2 g / cm.

7. The polyurethane composite material according to claim 1 or 2, wherein the polyurethane composite material is formed in the form of a sheet having a thickness of 0.5 to 10 mm.

8. The polyurethane composite material according to claim 1 or 2, comprising a flame retardant (d) selected from the group consisting of expandable graphite, red phosphorus, ammonium polyphosphate, triethyl phosphate, tris(2-chloroisopropyl) phosphate, melamine, expandable graphite (EG), red phosphorus, ammonium polyphosphate, tris(1-chloro-2-propyl) phosphate (TCPP), triethyl phosphate (TEP), chlorine- and bromine-containing polyols such as epichlorohydrin, chlorendic anhydride, trichlorobutylene oxide (TCBO), phosphorus-containing polyols such as esters of orthophosphoric acid, esters of phosphoric acid, phosphanate polyols, phosphine oxide polyols and phosphoramide polyols.

9. The polyurethane composite material according to claim 1 or 2, wherein the polyurethane composite material passes the UL94 V0 grade of the fire resistance test.

10. A method for producing the polyurethane composite material according to claim 1, comprising: 1) providing reinforcing fibers in the form of a continuous phase; 2) the following materials, (b) at least one polyol reactive with isocyanate, (c) optionally a chain extender and / or a crosslinking agent, (d) a flame retardant, (e) optionally a filler, (f) a blowing agent, (g) a catalyst, and (h) optionally additives and / or auxiliaries preparing a polyol component by mixing in a tank at a temperature of 20 to 80°C; 3) mixing the polyol component obtained in step 2) with an isocyanate component and optionally reinforcing fibers in the form of a discontinuous phase at a temperature of 20 to 80°C to obtain a mixture; 4) spraying or injecting the mixture obtained in step 3) onto the reinforcing fibers in the form of the continuous phase provided in step 1) by a first nozzle or injection head, and optionally spraying the reinforcing fibers in the form of a discontinuous phase onto the reinforcing fibers in the form of the continuous phase provided in step 1) by a second nozzle to obtain a sprayed or injected product; 5) hot pressing the sprayed or injected product obtained in step 4) in a mold having a temperature of 40 to 180°C under a hot press clamping force of 100 to 2000 tons; and 6) demolding and optionally trimming. comprising The polyurethane composite material obtained in step 6) contains 35 to 75% by mass of reinforcing fibers and 25 to 65% by mass of polyurethane foam, based on the total mass of the polyurethane composite material. The reinforcing fibers contain 75 to 100% by mass of reinforcing fibers in the form of a continuous phase and 0 to 25% by mass of reinforcing fibers in the form of a discontinuous phase, based on the total mass of the reinforcing fibers. The reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers, and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers. Method for producing a polyurethane composite material.

11. The method according to claim 10, wherein the reinforcing fibers in the form of a discontinuous phase in step 3) are obtained by cutting long fibers on site, added to the mixture of the isocyanate component and the polyol component of polyurethane at a certain ratio, and the cut reinforcing fibers have a length of 6 to 100 mm.

12. The method according to claim 10, wherein the reinforcing fibers in the form of a continuous phase in step 1) are in the form of a mat, a woven fabric, or a combination thereof.

13. A coated article comprising the polyurethane composite material according to claim 1 or 2, or the polyurethane composite material obtained by the production method according to claim 10.

14. The coated article according to claim 13, further comprising at least one metal sheet disposed on at least one side of the PU composite material.

15. The coated article according to claim 14, comprising two metal sheets disposed on both sides of the PU composite material.

16. The coated article according to claim 14, wherein the metal sheet is selected from aluminum alloy, iron, steel, and aluminum sheet.

17. The coated article according to claim 14, wherein the metal sheet has a thickness of 0.08 to 1.2 mm.

18. The coated article according to claim 14, wherein the metal sheet has a thickness of 0.2 to 1.2 mm, preferably 0.5 to 1.0 mm.

19. A laminated product, at least one heat insulating layer, and at least two layers of the polyurethane composite material according to claim 1 or 2 or the polyurethane composite material produced by the method according to claim 10 disposed on both sides of the heat insulating layer The laminated product, wherein the heat insulating layer contains a binder and a heat insulating material dispersed in the binder.

20. The laminated product according to claim 19, wherein the heat insulating layer contains 10% to 70% by mass, preferably 20% to 50% by mass, of the heat insulating material based on the total mass of the heat insulating layer.

21. The heat-insulating layer has a surface density of 50 g / m 2 to 500 g / m 2 and the laminated product according to claim 19.

22. The laminated product according to claim 19, wherein the heat insulating layer is an expandable heat insulating layer, the heat insulating material is an expandable heat insulating material, and it is selected from a phosphorus-containing material, a nitride-containing material, a sulfur-containing material, a boron-containing material, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, expandable graphite (EG), pentaerythritol, kaolin, or a combination thereof.

23. The laminated product according to claim 22, wherein the expandable graphite has an average particle size of 50 μm to 500 μm.

24. The laminated product according to claim 19, wherein the binder is selected from polyurethane, epoxy resin, polyethylene, polypropylene, polystyrene, or a combination thereof.

25. The laminated product according to claim 24, wherein the binder is polyurethane, and the polyurethane is a reaction product of a reaction mixture containing an isocyanate and a polyol reactive with the isocyanate, and the polyol reactive with the isocyanate contains a polyol having a mass average molecular weight of 1000 to 10000, preferably 4000 to 6000.

26. The laminated product according to claim 25, wherein the polyol reactive with the isocyanate has a functionality of 2 to 3.

27. The laminated product according to claim 19, wherein the laminated product has a foaming ratio of 5 to 20 times.

28. The laminated product according to claim 19, further comprising at least one base material layer disposed between the heat insulating layer and the polyurethane composite material layer, and the base material layer includes a fiber sheet, a plastic sheet, and a metal sheet.

29. The laminated product according to claim 19, further comprising at least a metal sheet disposed on the side surface of the laminated product.

30. A method for manufacturing the laminated product according to claim 19, comprising: 1) i) Mixing a heat insulating material and a binder, ii) Applying the mixture of step i) to the surface of a base material and curing the mixture, iii) Optionally removing the base material to provide a heat insulating layer; 2) Providing reinforcing fibers in the form of a continuous phase disposed on both sides of the heat insulating layer obtained in step 1); 3) The following materials (b) At least one polyol reactive with an isocyanate, (c) Optionally a chain extender and / or a crosslinking agent, (d) A flame retardant, (e) Optionally a filler, (f) A foaming agent, (g) A catalyst, and (h) Optionally additives and / or auxiliaries A step of preparing a polyol component by mixing in a tank at a temperature of 20 to 80 °C, 4) A step of obtaining a mixture by mixing the polyol component obtained in step 3) with an isocyanate component and optionally reinforcing fibers in the form of a discontinuous phase at a temperature of 20 to 80 °C, 5) A step of spraying or injecting, by means of a first nozzle or injection head, the mixture obtained in step 4) onto reinforcing fibers in the form of a continuous phase arranged on both sides of the heat insulation layer provided in step 2), and optionally, spraying reinforcing fibers in the form of a discontinuous phase onto the reinforcing fibers in the form of a continuous phase provided in step 2) by means of a second nozzle to obtain a sprayed or injected product, 6) A step of hot pressing the sprayed or injected product obtained in step 5) in a mold having a temperature of 40 to 180 °C under a hot pressing clamping force of 100 to 2000 tons, and 7) A step of demolding and optionally trimming to obtain a laminated product containing a polyurethane composite material arranged on both sides of the heat insulation layer relates to a method for manufacturing the laminated product, wherein the polyurethane composite material contains 35 to 75% by mass of reinforcing fibers and 25 to 65% by mass of polyurethane foam based on the total mass of the polyurethane composite material, the reinforcing fibers contain 75 to 100% by mass of reinforcing fibers in the form of a continuous phase and 0 to 25% by mass of reinforcing fibers in the form of a discontinuous phase based on the total mass of the reinforcing fibers, and the reinforcing fibers are selected from the group consisting of glass fibers, basalt fibers, carbon fibers, and natural fibers, preferably glass fibers and basalt fibers, more preferably glass fibers, A method for manufacturing a laminated product.

31. The method according to claim 30, wherein the reinforcing fibers in the form of a discontinuous phase in step 4) are obtained by cutting long fibers on site, added to a mixture of the isocyanate component and the polyol component of polyurethane at a certain ratio, and the cut reinforcing fibers have a length of 6 to 100 mm.

32. The method according to claim 30, wherein the reinforcing fibers in the form of a continuous phase in step 1) are in the form of a mat, woven fabric, or a combination thereof.

33. A coated article suitable for a battery system, comprising the laminated product according to claim 19.

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