Laminated part containing hard polyurethane outer layer and preparation method thereof

Abstract

A laminated part is described comprising a core, fiber layers arranged on each side of the core and impregnated with a polyurethane resin, and a polyurethane outer layer. The polyurethane outer layer comprises a cured reaction product of a reaction mixture comprising a polyisocyanate and an isocyanate reactive composition having a total hydroxyl number of from 300 to 700 mg KOH / g. The isocyanate reactive composition comprises: (i) a polyether polyol having a hydroxyl functionality of from 2 to 4 and a hydroxyl value of from 20 to 60 mg KOH / g; (ii) a polyol having a hydroxyl functionality of from 1.5 to 5.0 and a hydroxyl value of from 200 to 600 mg KOH / g, comprising an amine-initiated polyether polyol; and (iii) a diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.2. Methods of making such laminated parts are also described.

Description

Technical Field

[0001] This specification generally relates to laminated components comprising a polyurethane outer layer, related polyurethane sandwich materials, methods for their manufacture, and their use in the preparation of automotive components such as load floors. The polyurethane outer layer is a rigid layer that resists deformation when exposed to high temperatures. Background Art

[0002] Fiber-reinforced sandwich panels are used in the preparation of various laminated automotive components such as load floors. These components are sometimes prepared by arranging fiber layers on each side of a honeycomb core and then impregnating the fiber layers with a polyurethane resin so that the layers are bonded together. Subsequently, the component is compression molded under heated conditions before the polyurethane resin cures. In some cases, an outer layer with Class A surface quality can be placed on one layer of polyurethane-impregnated fiber layer and other layers (such as fabric layers) can be placed on the other layer.

[0003] However, in some applications, it may be desirable to provide a rigid outer layer for laminated automotive components such as load floors. Such a rigid outer layer can make it suitable for use as a mobile work surface, such as a workbench. However, for practical use, the rigid outer layer must be able to resist deformation when exposed to high temperatures (such as those that may be encountered in automotive applications). In addition, the rigid layer must be prepared using a composition with specific properties (such as reactive properties) that can be successfully applied using reaction injection molding technology (RIM process), which is commonly used in the preparation of fiber-reinforced sandwich panels.

[0004] The present invention has been made in view of the above circumstances. Summary of the Invention

[0005] In certain aspects, the present disclosure relates to a laminated component. The laminated component comprises: (a) a core; (b) fiber layers disposed on each side of the core and impregnated with a polyurethane resin; and (c) a polyurethane outer layer that is different from the polyurethane-impregnated fiber layer and is deposited on at least a portion of at least one polyurethane-impregnated fiber layer. The polyurethane outer layer comprises a cured reaction product of a reaction mixture comprising: (1) a polyisocyanate, and (2) an isocyanate-reactive composition having a total hydroxyl value of 300 to 700 mg KOH / g. The isocyanate-reactive composition comprises: (i) a polyether polyol having a hydroxyl functionality of 2 to 4 and a hydroxyl value of 20 to 60 mg KOH / g, (ii) a polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g, which comprises an amine-initiated polyether polyol; and (iii) a diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.2.

[0006] In other aspects, the present disclosure relates to a method of preparing a laminated component. The method includes: (a) inserting a sandwich structure into a mold cavity, wherein the sandwich structure includes: (1) a core, and (2) fiber layers disposed on each side of the core, each fiber layer being impregnated with a polyurethane resin; (b) closing the mold; (c) injecting a reaction mixture for forming polyurethane into the cavity by a RIM process; (d) reacting the reaction mixture in the closed mold to form a polyurethane outer layer, which is deposited on at least a portion of at least one polyurethane-impregnated fiber layer; (e) opening the mold; and (f) removing the laminated component from the opened mold. In these methods, the reaction mixture for forming polyurethane comprises: (1) a polyisocyanate; and (2) an isocyanate-reactive composition having a total hydroxyl value of 300 to 700 mg KOH / g, wherein the isocyanate-reactive composition comprises: (i) a polyether polyol having a hydroxyl functionality of 2 to 4 and a hydroxyl value of 20 to 60 mg KOH / g, (ii) a polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g, which includes an amine-initiated polyether polyol, and (iii) a diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.2. Detailed Description

[0007] This specification recites and describes various embodiments to provide a comprehensive understanding of the structure, function, characteristics, and uses of the disclosed invention. It should be understood that the various embodiments recited and described in this specification are non-limiting and non-exhaustive. Thus, the present invention is not limited by the descriptions of the various non-limiting and non-exhaustive embodiments disclosed in this specification. The features and characteristics described in connection with the various embodiments may be combined with the features and characteristics of other embodiments. Such modifications and variations are intended to be covered within the scope of this specification. Accordingly, the claims may be modified to recite any feature or characteristic that is explicitly or inherently described in this specification or otherwise explicitly or inherently supported by this specification. In addition, the applicant reserves the right to modify the claims to disclaim any feature or characteristic that may exist in the prior art. Thus, any such modification complies with the requirements of 35 U.S.C. § 112 and 35 U.S.C. § 132(a). The various embodiments disclosed and described in this specification may include the features and characteristics described herein in various ways, consisting of or consisting essentially of such features and characteristics.

[0008] Unless otherwise indicated, the entire content of any patent, publication, or other publicly available material identified herein is incorporated by reference into this specification only to the extent that the incorporated material does not conflict with the existing definitions, statements, or other publicly available material expressly set forth in this specification. Accordingly, and to the extent necessary, the expressly set forth disclosure in this specification supersedes any conflicting material incorporated herein by reference. Any material or portion thereof that is said to be incorporated by reference into this specification but which conflicts with the existing definitions, statements, or other publicly available material set forth herein is incorporated only to the extent that the incorporated material does not conflict with the existing publicly available material. The applicant reserves the right to amend this specification to expressly recite any subject matter or portion thereof incorporated herein by reference.

[0009] In this specification, unless otherwise indicated, all numerical parameters should be understood to be prefaced and qualified in all instances by the term "about", in view of the inherent variability of the underlying measurement techniques used to determine the value of the parameter. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter set forth in this specification should be construed in light of the number of significant digits recorded and by application of ordinary rounding techniques.

[0010] In addition, any numerical range recited in this specification is intended to include all sub-ranges having the same numerical precision subsumed within the recited range. For example, the range "1.0 to 10.0" is intended to include all sub-ranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, all sub-ranges having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as 2.4 to 7.6. Any maximum numerical limitation recited in this specification is intended to include all lower numerical limitations subsumed therein, and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, the applicant reserves the right to amend this specification (including the claims) to expressly recite any sub-range subsumed within the ranges expressly recited herein. All such ranges are intended to be inherently described in this specification such that amendments to expressly recite any such sub-range would satisfy the requirements of 35 U.S.C. § 112 and 35 U.S.C. § 132(a).

[0011] Unless otherwise specified, the grammatical articles “a,” “an,” and “the” used in this specification are intended to include “at least one” or “one or more.” Thus, the articles are used in this specification to refer to one or more than one (i.e., to “at least one”) of the grammatical object of the article. For example, “a component” refers to one or more components, and thus, more than one component may be contemplated and more than one component may be employed or used in the practice of the described embodiments. Further, the use of a singular noun includes the plural, and the use of a plural noun includes the singular, unless the context in which it is used otherwise requires.

[0012] As used herein, the term “functionality” refers to the average number of reactive hydroxyl groups (OH) present per molecule of polyol and refers to the theoretical average nominal functionality of the polyol, i.e., the functionality calculated based on the average number of hydroxyl groups per molecule of initiator used to prepare the polyol and their relative amounts. In the preparation of polyurethanes, the hydroxyl groups react with the isocyanate groups (-NCO) attached to the isocyanate compound. The term “hydroxyl value” refers to the number of reactive hydroxyl groups available for reaction and is expressed as the milligrams of potassium hydroxide equivalent to the hydroxyl content of one gram of polyol, which is determined according to ASTM D4274-16. The term “equivalent weight” refers to the weight of a compound divided by its valence. For a polyol, the equivalent weight refers to the weight of the polyol that will combine with an isocyanate group and can be calculated by dividing the molecular weight of the polyol by its functionality. The equivalent weight of a polyol can also be calculated by dividing 56,100 by the hydroxyl value of the polyol — equivalent weight (g / eq) = (56.1 x 1000) / hydroxyl value. As used herein, the equivalent weight and molecular weight of a polymer are the number-average equivalent weight and number-average molecular weight, respectively.

[0013] As described, certain embodiments of this specification relate to laminated components. These laminated components include a core. The core can be composed of metal, plastic, natural materials, and / or paper. Suitable metals include aluminum, magnesium, and their alloys. Suitable plastics include polyamides, polyesters, polycarbonates, polypropylenes, polystyrenes, ABS, polyamide-imides (PAI), and mixtures thereof. The plastics can be reinforced or non-reinforced, filled or non-filled. Examples of natural materials are wood, linen, sisal, jute, and hemp. As used herein, the term “paper” refers to any type of paper, including multi-layer paper, cardboard, and resin-impregnated paper.

[0014] In some embodiments, the core has a large number of cavities. The cavities can be of any geometric shape. For example, they can be angular or circular channels, pores, or bubbles. The cavities can be arranged regularly or irregularly. In some embodiments, the core has a corrugated, angular, honeycomb, or foamed profile. For example, the core can be corrugated metal or corrugated cardboard. Similar to corrugated metal or corrugated cardboard, the core can also be angular instead of corrugated, such as in a rectangular or triangular shape. Additionally, similar to corrugated metal or corrugated cardboard, the core can also be made of plastic. For example, angular or corrugated plastic profiles can be extruded. For example, a multi-wall sheet can also be used as a plastic core.

[0015] In some embodiments, the thickness of the core is 5 to 50 millimeters. Due to the large number of cavities, the weight of the core may be relatively low relative to its thickness. In some embodiments, the density of the core is 10 to 1000 kg / m 3 .

[0016] The laminated components in this specification include fiber layers disposed on each side of the core. Suitable fiber layers include, for example: glass fiber mats, chopped glass fiber rovings mats, random glass fiber layers, glass fiber fabrics, cut or shredded glass fibers or mineral fibers, natural fiber mats and knitted fabrics, cut natural fibers and fiber mats, non-woven fabrics and knitted fabrics based on polymer, carbon, or aramid fibers, and mixtures thereof. Natural materials suitable for the fiber layers include, but are not limited to, flax, sisal, jute, and hemp. The fiber layers on each side of the core can be the same or different.

[0017] These fiber layers are disposed on or applied to both sides of the core and impregnated with a polyurethane resin. In some embodiments, the thickness of the fiber layer is 0.1 to 2 millimeters. In some embodiments, the unit area weight of the fiber layer is 225 to 1200 g / m 2 .

[0018] The polyurethane resin at least partially penetrates the fiber layer and the core, thereby impregnating the fiber layer. Thus, in some embodiments, the polyurethane resin partially or completely fills the cavities of the core. The polyurethane resin is used to bond the layers together, and these layers are pressed into shape under heated conditions before the polyurethane resin cures. The polyurethane resin fixes the fibers and forms the surface of the composite component, thereby imparting high strength and stiffness to it by bonding the layers together. This composite material comprising a core and fiber layers impregnated with polyurethane resin disposed on each side of the core is also referred to herein as a "sandwich structure".

[0019] The polyurethane resin system used to impregnate the fiber layer can be a single-component system or a multi-component system (such as a two-component system). It can be foamed or non-foamed.

[0020] In some embodiments, the polyurethane resin impregnating the fiber layer comprises the reaction product of a reaction mixture comprising: (1) at least one polyisocyanate; (2) at least one polyol component having an average hydroxyl value of from 300 to 700, which in some embodiments comprises at least one short-chain polyol and one long-chain polyol, and the initial polyol has a hydroxyl functionality of from 2 to 6; (3) water; (4) an activator; (5) a stabilizer; and, optionally (6) other auxiliary materials, mold release agents, and additives.

[0021] Suitable polyol components include, but are not limited to, polyols having at least two hydrogen atoms reactive with isocyanate groups, such as polyester polyols and polyether polyols.

[0022] Suitable polyisocyanates include, but are not limited to, polymeric isocyanates of the diphenylmethane diisocyanate series (pMDI type), their prepolymers, or crude MDI.

[0023] In certain embodiments, water is used in an amount of from 0.1 to 3.0 parts, such as from 0.3 to 2.0 parts, per 100 parts of the polyol formulation.

[0024] Conventional activators (such as amines or metal salts) for the expansion and crosslinking reactions can be used for catalysis.

[0025] Suitable foam stabilizers include polyether siloxanes, including water-soluble polyether siloxanes. These compounds typically have copolymers of ethylene oxide and propylene oxide bonded to polydimethylsiloxane groups. Such foam stabilizers are described, for example, in U.S. Patent Nos. 2,834,748, 2,917,480, and 3,629,308, the disclosures of which are incorporated herein by reference. Polyorganosiloxane-polyoxyalkylene copolymers branched by urethane groups as described in U.S. Patent Nos. 4,096,162 and 4,163,830 are also suitable, the disclosures of which are incorporated herein by reference.

[0026] Other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oil, castor oil esters or ricinoleic acid esters, Turkey red oil, and peanut oil, as well as cell regulators such as paraffin, fatty alcohols, and dimethylpolysiloxane are also suitable. Oligomeric polyacrylates having polyoxyalkylene and fluoroalkane groups as side groups are also suitable for improving and / or stabilizing emulsification, filler dispersion, and porous structure. Surfactants are generally used in an amount of from 0.01 to 5 parts by weight per 100 parts by weight of the polyol.

[0027] In the reaction mixture for preparing the polyurethane resin, other auxiliary materials, release agents, and additives can be optionally added. These include, for example, surface-active additives such as emulsifiers, flame retardants, chain extenders, crosslinking agents, nucleating agents, antioxidants, lubricants and release agents, dyes, dispersion aids, and pigments.

[0028] In some embodiments, the components react in amounts such that the equivalent ratio of the NCO groups in the polyisocyanate component (1) to the total number of hydrogens in components (2) and (3) and optionally (5) that are reactive with the isocyanate groups is from 0.8:1 to 1.4:1, for example from 0.9:1 to 1.3:1.

[0029] In some embodiments, the unit area weight of the cured polyurethane resin impregnating the fiber layer is from 400 to 1200 g / m 2 .

[0030] The above sandwich structure can be prepared, for example, by applying the fiber layer to each side of the core and applying the initial polyurethane components to the fiber layer. Alternatively, suitable mixing head techniques can also be used to introduce the fibers onto the core by the flow of the polyurethane raw materials. The polyurethane resin can be prepared, for example, by the one-shot process or the prepolymer process.

[0031] As previously mentioned, the laminated component in this specification further includes a polyurethane outer layer, which is different from the polyurethane-impregnated fiber layer and is deposited on at least a part of at least one layer of the polyurethane-impregnated fiber layer. The polyurethane outer layer contains the cured reaction product of the reaction mixture for forming the polyurethane, and the reaction mixture contains organic diisocyanates and / or polyisocyanates (collectively sometimes referred to herein as "isocyanates").

[0032] Suitable isocyanates for preparing the polyurethane outer layer include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic polyisocyanates. Exemplary isocyanates are those having the following formula:

[0033] Q(NCO) n

[0034] where n is 2, 3, or 4, and Q is an aliphatic hydrocarbon group having 2 to 18 carbon atoms, for example 6 to 10 carbon atoms, a cycloaliphatic hydrocarbon group having 4 to 15 carbon atoms, for example 5 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, for example 6 to 13 carbon atoms, or an araliphatic hydrocarbon group having 8 to 15 carbon atoms, for example 8 to 13 carbon atoms.

[0035] In some embodiments, the isocyanate includes ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate and 1,4-cyclohexane diisocyanate and any mixture of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4-hexahydrotoluene diisocyanate and 2,6-hexahydrotoluene diisocyanate and any mixture of these isomers, hexahydro-1,3-phenylene diisocyanate and hexahydro-1,4-phenylene diisocyanate, perhydro-2,4'-diphenylmethane diisocyanate and perhydro-4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 1,4-tetraethylbenzene diisocyanate (DDI), 4,4'-stilbene diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate (TODI), 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI) and any mixture of these isomers, diphenylmethane-2,4'-diisocyanate and / or diphenylmethane-4,4'-diisocyanate (MDI), naphthylene-1,5-diisocyanate (NDI), or a mixture of any two or more thereof.

[0036] Other suitable isocyanates include triphenylmethane-4,4',4''-triisocyanate, polyphenyl-polymethylene polyisocyanate (such as obtained by condensing aniline and formaldehyde and then phosgenating), m-isocyanatophenylsulfonyl isocyanate and p-isocyanatophenylsulfonyl isocyanate, perchlorinated aryl polyisocyanate, polyisocyanate having a carbodiimide group, norbornane diisocyanate, polyisocyanate having a urethane group, polyisocyanate having an isocyanurate group, polyisocyanate having a carbamate group, polyisocyanate having an acylated urea group, polyisocyanate having a biuret group, polyisocyanate prepared by telomerization reaction, polyisocyanate having an ester group, reaction product of the above isocyanate and acetal, and polyisocyanate containing a polymer fatty acid ester.

[0037] Of course, a mixture of two or more of the above polyisocyanates can also be used.

[0038] However, in some embodiments, the isocyanate includes 2,4-toluene diisocyanate and 2,6-toluene diisocyanate and any mixture of these isomers ("TDI"), 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and polyphenyl-polymethylene polyisocyanate prepared by condensing aniline and formaldehyde and then phosgenating ("crude MDI"), and polyisocyanates having carbodiimide groups, uretonimine groups, urethane groups, allophanate groups, isocyanurate groups, urea groups, or biuret groups ("modified polyisocyanates"), especially such modified polyisocyanates derived from 2,4-toluene diisocyanate and / or 2,6-toluene diisocyanate or derived from 4,4'-diphenylmethane diisocyanate and / or 2,4'-diphenylmethane diisocyanate. Naphthylene-1,5-diisocyanate and mixtures of the said polyisocyanates are also suitable.

[0039] In some embodiments, the isocyanate includes a prepolymer having isocyanate groups prepared by reacting a polyol and / or a chain extender and / or a crosslinker with at least one aromatic diisocyanate selected from TDI, MDI, TODI, DIBDI, NDI, and DDI (such as 4,4'-MDI) to prepare an addition polymer having urethane groups and isocyanate groups, wherein the NCO content is 6 to 25% by weight.

[0040] In certain embodiments, the polyisocyanate includes a methylene-bridged polyphenyl polyisocyanate and / or a prepolymer of a methylene-bridged polyphenyl polyisocyanate, having an average functionality of 1.8 to 3.5 isocyanate moieties per molecule, such as 2.0 to 3.1 isocyanate moieties, and an NCO content of 20 to 32% by weight.

[0041] The reaction mixture for forming a polyurethane outer layer deposited on at least a portion of at least one polyurethane-impregnated fiber layer further comprises an isocyanate-reactive composition having a total hydroxyl value of 300 to 700 mg KOH / g, such as 300 to 500 mg KOH / g, or in some cases 300 to 400 mg KOH / g.

[0042] The isocyanate-reactive composition comprises a polyether polyol having a hydroxyl functionality of 2 to 4, such as 2.5 to 3.5 or 2.8 to 3.2, and a hydroxyl value of 20 to 60 mg KOH / g, such as 20 to 50 mg KOH / g or 25 to 40 mg KOH / g.

[0043] Such polyether polyols can be prepared, for example, by reacting alkylene oxides (such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin, optionally in the form of a mixture or sequentially) with a starting component ("initiator") having reactive hydrogen atoms (such as water, alcohol, ammonia or amine). Depending on the method control, such polyether polyols can be homopolymers, block copolymers, random copolymers, capped polymers or polymers capped with a mixture of different epoxides. Specific examples of suitable initiators for preparing such polyether polyols include, but are not limited to, compounds having two or more hydroxyl groups, such as water, 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose, castor oil, modified soybean oil. The initiator compounds can be used alone or in the form of a mixture.

[0044] In some embodiments, the propylene oxide content of the polyether polyol having a functionality of 2 to 4 and an OH value of 20 to 60 mg KOH / g is 70 to 90 wt% or 75 to 85 wt%, and the ethylene oxide content is 10 to 30 wt% or 15 to 25 wt%, based on the total weight of the alkylene oxides used to prepare the polyether polyol.

[0045] In addition, in some embodiments, the polyether polyol having a functionality of 2 to 4 and an OH value of 20 to 60 mg KOH / g is present in an amount of at least 30 wt%, such as 30 to 50 wt% or 30 to 40 wt%, based on the total weight of the isocyanate-reactive composition used to prepare the polyurethane outer layer.

[0046] As described above, the isocyanate-reactive composition in the reaction mixture for forming the polyurethane outer layer further comprises a polyol having a hydroxyl functionality of 1.5 to 5.0 (such as 2 to 4) and a hydroxyl value of 200 to 600 mg KOH / g (such as 300 to 400 mg KOH / g). In some embodiments, the polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g is present in an amount of at least 20 wt%, such as 20 to 60 wt%, 30 to 50 wt% or 40 to 50 wt%, based on the total weight of the isocyanate-reactive composition.

[0047] Suitable such polyols having a hydroxyl functionality of 1.5 to 5.0 (such as 2 to 4) and a hydroxyl value of 200 to 600 mg KOH / g include, but are not limited to, polyether polyols, polyester polyols and mixtures thereof.

[0048] For example, in some embodiments, polyols having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g include amine-initiated polyether polyols, such as aromatic amine-initiated polyether polyols.

[0049] As used herein, "aromatic amine-initiated polyether polyol" refers to a polyether polyol that is a reaction product of an H-functional initiator comprising an aromatic amine (such as toluenediamine ("TDA")) and an alkylene oxide. In certain embodiments, the amine functionality of the aromatic amine used is at least 1, such as 1 to 3 or 1 to 2. Specific examples of suitable aromatic amines that can be used include: crude TDA obtained by reduction after nitration of toluene; 2,3-TDA, 3,4-TDA, 2,4-TDA, 2,6-TDA, or mixtures thereof; aniline; 4,4'-methylenedianiline; methylene-bridged polyphenyl polyamines composed of isomers of methylenedianiline and triamines, or higher molecular weight polyamines prepared by reacting aniline with formaldehyde by methods known in the art. In some embodiments, a mixture composed of 2,3-TDA and 3,4-TDA (commonly referred to as "o-TDA") is used.

[0050] In addition to aromatic amines, other H-functional initiators can also be used to prepare aromatic amine-initiated polyether polyols. These other H-functional initiators include, for example, water, propylene glycol, glycerol, ethylene glycol, ethanolamine, diethylene glycol, or mixtures of any two or more thereof. It is understood that multiple individual initiators can be used in combination with each other. However, in some embodiments, the aromatic amine is the main or substantially sole H-functional initiator used to prepare the aromatic amine-initiated polyether polyol. This means that in these embodiments, the aromatic amine is present in an amount greater than 50% by weight, such as at least 80% by weight, at least 90% by weight, or even 100% by weight, based on the total weight of the H-functional initiators used to prepare the aromatic amine-initiated polyether polyol.

[0051] Any of a variety of alkylene oxides can be used to prepare amine-initiated polyether polyols (e.g., aromatic amine-initiated polyether polyols), such as ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, and mixtures thereof. The alkylene oxides can be added individually, added sequentially to form blocks, or added as a mixture to form heteric polyethers. Aromatic amine-initiated polyether polyols can have primary or secondary hydroxyl end groups. In some embodiments, propylene oxide is the initial alkylene oxide used to prepare the aromatic amine-initiated polyether polyol. This means that in these embodiments, the amount of propylene oxide is more than 50% by weight, such as at least 60% by weight, 60 to 90% by weight, 60 to 80% by weight, or 60 to 70% by weight, based on the total weight of the alkylene oxides used to prepare the aromatic amine-initiated polyether polyol. In some embodiments, ethylene oxide is used in a relatively small amount. Thus, in these embodiments, ethylene oxide is present in an amount of no more than 50% by weight, such as no more than 40% by weight, 10 to 40% by weight, 20 to 40% by weight, or 30 to 40% by weight, based on the total weight of the alkylene oxides used to prepare the aromatic amine-initiated polyether polyol.

[0052] In addition, in some embodiments, the amine-initiated polyether polyol (e.g., aromatic amine-initiated polyether polyol) is present in an amount of 1 to 20% by weight, 5 to 15% by weight, or 8 to 12% by weight, based on the total weight of the isocyanate-reactive composition.

[0053] In some embodiments, polyols having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g include polyol-initiated (e.g., aliphatic polyol-initiated) polyether polyols that are different from the aforementioned amine-initiated polyether polyols. In some cases, the hydroxyl value of such polyol-initiated polyether polyols is 200 to 500 mg KOH / g, 200 to 400 mg KOH / g, 200 to 300 mg KOH / g, 200 to 250 mg KOH / g, 230 to 250 mg KOH / g, or in some cases 233 to 243 mg KOH / g, and the functionality is greater than 2 to 4, such as 2.5 to 3.5, or in some cases 3.0.

[0054] As used herein, "aliphatic polyol-initiated polyether polyol" refers to a polyether polyol that is a reaction product of an H-functional initiator comprising an aliphatic alcohol and an alkylene oxide. Such aliphatic alcohols include aliphatic diols, triols, and / or higher polyols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, and glycerol, including mixtures of any two or more thereof. In addition to aliphatic alcohols, other H-functional initiators can be used to prepare polyol-initiated polyether polyols, including, for example, the amines mentioned above with respect to amine-initiated polyether polyols. However, in some embodiments, the aliphatic alcohol is the primary or substantially sole H-functional initiator used to prepare the polyol-initiated polyether polyol. This means that, in these embodiments, the aliphatic alcohol is present in an amount greater than 50% by weight, such as at least 80% by weight, at least 90% by weight, or even 100% by weight, based on the total weight of the H-functional initiator used to prepare the polyol-initiated polyether polyol. In some embodiments, the aliphatic alcohol initiator comprises glycerol, or in some cases consists of glycerol; the alkylene oxide comprises propylene oxide, or in some cases consists of propylene oxide.

[0055] In certain embodiments, the aforementioned polyol-initiated polyether polyol is present in an amount of 10 to 30% by weight, such as 15 to 25% by weight, or 15 to 20% by weight, based on the total weight of the isocyanate-reactive composition. In certain embodiments, the polyol-initiated polyether polyol and the amine-initiated polyether polyol are present in a weight ratio of at least 1:1, such as 1:1 to 5:1, 1:1 to 2:1, or in some cases 1.5:1 to 2:1.

[0056] In addition, in some embodiments, polyols having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g include aromatic polyester polyols. Suitable aromatic polyester polyols include, for example, the reaction products of aromatic diacids or aromatic anhydrides with suitable diols or triols. For example, the polyester polyol can be a reaction product of a diol and / or triol (such as ethylene glycol, propylene glycol, butanediol, 1,3-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, trimethylolethane, trimethylolpropane, pentanediol, hexanediol, heptanediol, 1,3-dihydroxymethylcyclohexane, and 1,4-dihydroxymethylcyclohexane or mixtures of two or more thereof) and an aromatic diacid or aromatic anhydride (such as phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, or mixtures of two or more thereof).

[0057] In certain embodiments, the OH value of the aromatic polyester polyol is from 150 to 410 mg KOH / g (such as from 200 to 360 mg KOH / g or from 300 to 360 mg KOH / g), and the functionality is from 1.5 to 3, such as from 1.9 to 2.5.

[0058] In some embodiments, the amount of the aromatic polyester polyol present is from 10 to 30% by weight, such as from 15 to 25% by weight, or from 15 to 20% by weight, based on the total weight of the isocyanate-reactive composition. In certain embodiments, the aromatic polyester polyol and the amine-initiated polyether polyol are present in the isocyanate-reactive composition in a weight ratio of at least 1:1, such as from 1:1 to 5:1, or in some cases from 1:1 to 2:1 or from 1.5:1 to 2:1.

[0059] In addition to the above polyols, the isocyanate-reactive composition for forming the polyurethane outer layer further comprises a diol having a molecular weight of from 62 to 399 g / mol (such as from 62 to 200 g / mol) and a hydroxyl functionality of from 1.8 to 2.2 (such as 2.0). Suitable but non-limiting examples of such diols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, butane-1,4-diol, butane-1,3-diol, butane-2,3-diol, pentane-1,5-diol, hexane-1,6-diol, 2,2-dimethylpropane-1,3-diol, 1,4-dihydroxycyclohexane, 1,4-bis(hydroxymethyl)cyclohexane, octane-1,8-diol, decane-1,10-diol, dodecane-1,12-diol, and mixtures of two or more thereof.

[0060] In some embodiments, the amount of the foregoing diol present is from 5 to 30% by weight, such as from 10 to 25% by weight, or from 15 to 25% by weight, based on the total weight of the isocyanate-reactive composition. In certain embodiments, the diol comprises a diol mixture comprising (i) a diol having a molecular weight of from 62 to 110 g / mol, and (ii) a diol having a molecular weight of from 111 to 200 g / mol, wherein the diol (i) and the diol (ii) are present in a weight ratio of at least 1:1, such as from 1:1 to 5:1 or from 1:1 to 2.1.

[0061] The reaction mixture for forming the polyurethane outer layer may further comprise other components, such as catalysts and other additives.

[0062] Suitable catalysts include amine catalysts, such as tertiary amines. Exemplary tertiary amines include triethylamine, triethylenediamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine and higher homologues, 1,4-diazabicyclo-[2,2,2]-octane, N-methyl-N'-dimethylaminoethylpiperazine, bis-(dimethylaminoalkyl)piperazine, N,N'-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N-diethylbenzylamine, bis-(N,N-diethylaminoethyl)adipate, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethyl-B-phenylethylamine, bis-(dimethylaminopropyl)urea, bis-(dimethylaminopropyl)amine, 1,2-dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic amidines, bis(dialkylamino)alkyl ethers (such as bis(dimethylaminoethyl) ether), and tertiary amines having an amide group (such as formamide group). Mannich bases composed of secondary amines (such as dimethylamine) and aldehydes (such as formaldehyde) or ketones (such as acetone, methyl ethyl ketone or cyclohexanone) and phenols (such as phenol, nonylphenol or bisphenol) are also suitable as catalysts. Tertiary amines having active hydrogen atoms related to isocyanate groups as catalysts are, for example, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, their reaction products with alkylene oxides (such as propylene oxide and / or ethylene oxide) and secondary and tertiary amines. Amines having a carbon-silicon bond (such as 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyltetramethyldisiloxane) can be used as catalysts. In addition, nitrogen-containing bases such as tetraalkylammonium hydroxide and hexahydrotriazine are also suitable catalysts.

[0063] In addition to, or in place of, the above amine catalysts, metal catalysts can also be used. Specific examples of such catalysts include organometallic compounds of tin, titanium, and bismuth, especially organotin compounds. Tin(II) salts of carboxylic acids can be used, such as tin(II) acetate, tin(II) octanoate, tin(II) ethylhexanoate, tin(II) laurate, and tin(IV) compounds, such as dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.

[0064] The reaction mixture for forming the polyurethane outer layer can contain various other additives. These additives include, but are not limited to, emulsifiers, foam stabilizers, cell regulators, flame retardants, UV stabilizers, nucleating agents, oxidation inhibitors, stabilizers, colorants, dispersants and pigments. However, in some embodiments, the reaction mixture for forming the polyurethane outer layer does not contain a blowing agent, so the polyurethane outer layer is a non-foamed polyurethane outer layer.

[0065] The reactivity characteristics of the reaction mixture and the physical properties of the cured reaction product are particularly suitable for the preparation of the rigid polyurethane outer layer of the laminated components of the type described herein. The outer layer is resistant to deformation when exposed to high temperatures and can advantageously be prepared using RIM technology. For example, the gel time of the reaction mixture at the processing temperature (the period from the moment of mixing the polyurethane composition to the moment when a fiber string can be pulled out of the polyurethane composition, sometimes also referred to as the fiber time or draw time) can be at least 15 seconds or at least 20 seconds and not more than 2 minutes, not more than 1 minute or not more than 30 seconds. In addition, the cured polyurethane outer layer can have a Shore D hardness of at least 70 or at least 75 (measured according to ASTM D2240-15(2021)), a tensile strength of at least 5,000 psi (measured according to ASTM D638-22), an elongation at break of at least 30% (measured according to ASTM D638-22), a flexural modulus of at least 225,000 psi (measured according to ASTM D 790-17) and / or a heat distortion temperature (HDT) above 140°F @ 66 psi (measured according to ASTM D648-18). The reaction mixture for forming polyurethane suitable for the preparation of the polyurethane outer layer described herein is commercially available and includes certain products available from Covestro LLC under the trade name including one or more of TB 100-15 and 100-30.

[0066] Certain embodiments of this specification relate to methods of manufacturing laminated components. These methods include providing a mold having a cavity therein. Suitable molds include, for example, molds made of aluminum or steel, or metal-sprayed epoxy molds.

[0067] To improve demolding, the inner wall of the mold used is optionally coated with an external mold release agent, such as a non-reactive, silicone-free external mold release agent, such as a non-transfer wax.

[0068] According to the methods in this specification, a sandwich structure of the aforementioned type is inserted into the mold cavity, and then the mold is closed. Then, a polyurethane outer layer deposited on at least a portion of at least one polyurethane-impregnated fiber layer of the sandwich structure is prepared by using reaction injection molding technology (RIM process). In certain embodiments, the amounts of the components of the reaction mixture for forming the polyurethane outer layer are selected such that the isocyanate index of the reaction mixture is from 70 to 130, such as from 80 to 120 or from 90 to 110. It should be understood that the "isocyanate index" means the quotient of the number of isocyanate groups and the number of isocyanate-reactive groups multiplied by 100.

[0069] In some embodiments, the initial temperature of the reaction mixture introduced into the mold is in the range of 20 to 80 °C, such as 30 to 70 °C, and in some embodiments, the temperature of the mold is in the range of 30 to 130 °C, such as 40 to 80 °C.

[0070] The methods described in this specification include: reacting a reaction mixture in a mold to form a polyurethane outer layer deposited on at least a portion of at least one polyurethane-impregnated fiber layer, and then removing the laminated component from the mold. In some embodiments, the molded laminated component is removed from the mold, i.e., demolded after an in-mold dwell time of 5 to 180 seconds. In some cases, conditioning can be carried out at a temperature of about 60 to 180 °C for 30 to 120 minutes after demolding.

[0071] As described, the polyurethane outer layer described herein is deposited on at least a portion of at least one polyurethane-impregnated fiber layer. In some embodiments, the polyurethane outer layer is deposited on two polyurethane fiber layers. In some embodiments, the polyurethane outer layer described herein completely or substantially completely coats one or two polyurethane-impregnated fiber layers. If the polyurethane outer layer described herein is not deposited on one of the polyurethane-impregnated fiber layers, another layer, such as a decorative layer, can be deposited thereon as needed. Such a layer can include, for example, a metal foil or sheet, a dense thermoplastic composite made of, for example, PMMA (polymethyl methacrylate), ASA (acrylate-modified styrene acrylonitrile terpolymer), PC (polycarbonate), PA (polyamide), PBT (polybutylene terephthalate), and / or PPO (polyphenylene oxide). Alternatively, such a layer can be composed of a fabric material with a barrier of a TPU (thermoplastic polyurethane) sheet, a dense or foamed plastic sheet, and other sprayed or RIM polyurethane surface layers.

[0072] In some embodiments, if the polyurethane outer layer described herein is not deposited on one of the polyurethane-impregnated fiber layers, a different polyurethane outer layer can be deposited on the other polyurethane-impregnated fiber layer. For example, in some embodiments, such a different polyurethane outer layer can have a Class A surface. Additionally, in some embodiments, such a different polyurethane layer can comprise the cured reaction product of a reaction mixture comprising: (1) a polyisocyanate; (2) a polyether polyol having a molecular weight of 800 Da to 25,000 Da and a functionality of 2 to 8; and (3) 0.5 to 15 wt% of a fatty acid ester based on the total weight of the reaction mixture, the fatty acid ester having an isocyanate-reactive functionality of at least 1 and a hydroxyl value of 10 to 20 mg KOH / g. Such polyurethane outer layers having a Class A surface are described in U.S. Patent No. 11,124,615B2, columns 5, line 65 to column 10, line 27, the cited portions of which are incorporated herein by reference.

[0073] Some suitable applications of the laminated component of the present invention in the automotive industry include, for example, roof, hood, fender, door or floor module, and load floor.

[0074] The following non - limiting and non - exhaustive examples are intended to further describe non - limiting and non - exhaustive embodiments without limiting the scope of the embodiments described in this specification.

[0075] Embodiment

[0076] The mold used for the experiments described below is a full - scale prototype load - floor tool. The mold is mounted on a press adjacent to a small cylindrical RIM machine. The mixing head is mounted in the middle of the tool for injecting RIM material. A pre - fabricated composite load - floor panel (comprising an inner honeycomb core and polyurethane - impregnated fiberglass layers arranged on each side of the core) is inserted into the tool, and the tool is closed under pressure. Then the RIM material is applied to one side of the panel. The tool is kept closed for two minutes before the finished component is removed. The mold is heated with a water pipe to 175°F. The heat is maintained by circulating water at the desired temperature through an electric thermostat device.

[0077] For the experiment, the mold cavity is cleaned with Chem Trend mold cleaner MOC - 10003 (N - methylpyrrolidone) to remove any residual external release agent, and then wiped with water to neutralize any residual mold cleaner. The mold cavity is treated with a release agent consisting of a solvent - based wax to facilitate the demolding of the rigid polyurethane outer layer to be prepared from the mold cavity. Then the panel is placed in the mold and the mold is closed, the panel having a paper honeycomb core and fiber layers arranged on each side of the core and impregnated with polyurethane resin.

[0078] For the experiment, the throughput of the RIM machine is set to 250 grams per second, and for the "B" polyol side (POLYOLSIDE), the material temperature is maintained at 95°F, and for the "A" isocyanate side (ISO SIDE), the material temperature is maintained at 90°F. The injection weight is set to a total of 1200 grams, and the material is injected into the tool. The high - pressure mixing head is connected to the middle of the tool, and the material is injected onto one side of the panel. The tool is kept closed for 120 seconds, then the two halves of the mold are separated and the mold is opened, and the component is demolded.

[0079] In addition to the amine scavenging catalyst and the black colorant, the "B" polyol side also contains a mixture of the following: (i) an aromatic polyester polyol in an amount of 10 to 30% by weight based on the total weight of the "B" polyol side, having a hydroxyl value of 150 to 410 mg KOH / g and a functionality of 1.5 to 3; (ii) a polyether polyol in an amount of 30 to 50% by weight based on the total weight of the "B" polyol side, having a hydroxyl value of 20 to 60 mg KOH / g and a functionality of 2 to 4; (iii) an aliphatic polyol-initiated polyether polyol in an amount of 10 to 30% by weight based on the total weight of the "B" polyol side, having a hydroxyl value of 200 to 500 mg KOH / g and a functionality greater than 2 to 4; (iv) an o-TDA-initiated polyether polyol in an amount of 1 to 20% by weight based on the total weight of the "B" polyol side, having a hydroxyl value of 200 to 400 mg KOH / g and a functionality of 1.5 to 5.0; and (v) a diol in an amount of 10 to 30% by weight based on the total weight of the "B" polyol side, having a molecular weight of 62 to 399 g / mol and a functionality of 1.8 to 2.2, said diol being a combination of the following diols: (1) two diols having a molecular weight of 62 to 110 g / mol and (2) one diol having a molecular weight of 111 to 200 g / mol, wherein diol (1) and diol (2) are present in a weight ratio of 1:1 to 2.1. The "A" isocyanate side is an aromatic polymeric isocyanate based on 4,4-diphenylmethane diisocyanate (MDI), having an NCO content of at least 31.0% by weight and a viscosity at 25 °C of 150 - 250 cps. The "B" polyol side is mixed with the "A" isocyanate side in a weight ratio of "B" polyol side : "A" isocyanate side of 100 : 85. The total hydroxyl value of the "B" polyol side is approximately 360 mg KOH / g.

[0080] The resulting polyurethane outer layer has a Shore D hardness of 78 (measured according to ASTM D2240 - 15(2021)), and an HDT of 178 °F @ 66 psi (measured according to ASTM D648 - 18).

[0081] Although the present invention has been described in detail above for purposes of illustration, it is to be understood that these details are for that purpose only and that those skilled in the art can make modifications thereto without departing from the spirit and scope of the invention, unless it may be limited by the claims.

Claims

1. A laminated component, comprising: (a) a core; (b) fiber layers disposed on each side of the core and impregnated with a polyurethane resin, and (c) a polyurethane outer layer, which is different from the polyurethane-impregnated fiber layers and which is deposited on at least a part of at least one polyurethane-impregnated fiber layer, wherein the polyurethane outer layer comprises the cured reaction product of a reaction mixture comprising (1) a polyisocyanate, and (2) an isocyanate-reactive composition having a total hydroxyl value of 300 to 700 mg KOH / g and comprising: (i) a polyether polyol having a hydroxyl functionality of 2 to 4 and a hydroxyl value of 20 to 60 mg KOH / g, (ii) a polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g, which comprises an amine-initiated polyether polyol; and (iii) a diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.

2.

2. The laminated component according to claim 1, wherein the core is made of paper, such as multi-layer paper, cardboard or resin-impregnated paper.

3. The laminated component according to claim 1 or claim 2, wherein the core comprises a cavity, such as wherein the core has a corrugated, angled, honeycomb or foamed profile.

4. The laminated component according to any one of claims 1 to 3, wherein the core has a thickness of 5 to 50 millimeters and / or a density of 10 to 1000 kg / m 3 .

5. The laminated component according to any one of claims 1 to 4, wherein the fiber layer comprises a glass fiber mat, a chopped glass fiber roving mat, a random glass fiber layer, a glass fiber fabric, cut or shredded glass fibers or mineral fibers, a natural fiber mat, a knitted fabric, cut natural fibers, non-woven fabrics and knitted fabrics based on polymer, carbon or aramid fibers, or mixtures thereof.

6. The laminated component according to any one of claims 1 to 5, wherein the thickness of the fiber layer is 0.1 to 2 millimeters and / or the basis weight of the fiber layer is 225 to 1200 g / m 2 .

7. The laminated component according to any one of claims 1 to 6, wherein the polyurethane resin impregnating the fiber layer comprises the reaction product of a reaction mixture comprising: (1) a polyisocyanate; (2) a polyol component having an average OH value of 300 to 700, which in some embodiments comprises at least one short-chain polyol and one long-chain polyol, and the initial polyol has a hydroxyl functionality of 2 to 6; (3) water; (4) an activator; (5) a stabilizer; and, optionally, (6) other auxiliary materials, mold release agents and additives.

8. The laminated component according to any one of claims 1 to 7, wherein the weight per unit area of the cured polyurethane resin impregnating the fiber layer is 400 to 1200 g / m 2 .

9. The laminated component according to any one of claims 1 to 8, wherein the polyisocyanate comprises a methylene-bridged polyphenyl polyisocyanate and / or a prepolymer of a methylene-bridged polyphenyl polyisocyanate, having an average functionality of 1.8 to 3.5, for example 2.0 to 3.1, isocyanate moieties per molecule and an NCO content of 20 to 32% by weight.

10. The laminated component according to any one of claims 1 to 9, wherein the total hydroxyl value of the isocyanate-reactive composition is 300 to 500 mg KOH / g or 300 to 400 mg KOH / g.

11. The laminated component according to any one of claims 1 to 10, wherein the hydroxyl functionality of the polyether polyol having a hydroxyl functionality of 2 to 4 and a hydroxyl value of 20 to 60 mg KOH / g is 2.5 to 3.5 or 2.8 to 3.2, and / or the hydroxyl value is 20 to 50 mg KOH / g or 25 to 40 mg KOH / g.

12. The laminated component according to any one of claims 1 to 11, wherein the polyether polyol having a hydroxyl functionality of 2 to 4 and a hydroxyl value of 20 to 60 mg KOH / g is a reaction product of an alkylene oxide such as ethylene oxide and / or propylene oxide with an initiator, the initiator including water, 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose, castor oil, modified soybean oil, or a mixture of any two or more thereof.

13. The laminated component according to any one of claims 1 to 12, wherein the propylene oxide content of the polyether polyol having a functionality of 2 to 4 and an OH value of 20 to 60 mg KOH / g is 70 to 90% by weight or 75 to 85% by weight, and the ethylene oxide content is 10 to 30% by weight or 15 to 25% by weight, based on the total weight of the alkylene oxides used for preparing the polyether polyol.

14. The laminated component according to any one of claims 1 to 13, wherein the amount of the polyether polyol having a functionality of 2 to 4 and an OH value of 20 to 60 mg KOH / g is at least 30% by weight, 30 to 50% by weight or 30 to 40% by weight, based on the total weight of the isocyanate-reactive composition used for preparing the polyurethane outer layer.

15. The laminated component according to any one of claims 1 to 14, wherein the polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g has a hydroxyl functionality of 2 to 4 and / or a hydroxyl value of 300 to 400 mg KOH / g.

16. The laminated component according to any one of claims 1 to 15, wherein the amount of the polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g is at least 20% by weight, 20 to 60% by weight, 30 to 50% by weight or 40 to 50% by weight, based on the total weight of the isocyanate-reactive composition.

17. The laminated component according to any one of claims 1 to 16, wherein the polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g includes amine-initiated polyether polyols, such as aromatic amine-initiated polyether polyols.

18. The laminated component according to claim 17, wherein the aromatic amine-initiated polyether polyol is a reaction product of an alkylene oxide and an H-functional initiator containing an aromatic amine, and the aromatic amine is, for example, 2,3-TDA and 3,4-TDA.

19. The laminated component according to claim 18, wherein the amount of the aromatic amine present is greater than 50% by weight, at least 80% by weight, at least 90% by weight or 100% by weight, based on the total weight of the H-functional initiator used to prepare the aromatic amine-initiated polyether polyol.

20. The laminated component according to claim 18 or claim 19, wherein the amount of propylene oxide present is greater than 50% by weight, at least 60% by weight, 60 to 90% by weight, 60 to 80% by weight or 60 to 70% by weight, based on the total weight of the alkylene oxide used to prepare the aromatic amine-initiated polyether polyol; and / or the amount of ethylene oxide present is not more than 50% by weight, not more than 40% by weight, 10 to 40% by weight, 20 to 40% by weight or 30 to 40% by weight, based on the total weight of the alkylene oxide used to prepare the aromatic amine-initiated polyether polyol.

21. The laminated component according to any one of claims 17 to 20, wherein the amount of the amine-initiated polyether polyol, such as the aromatic amine-initiated polyether polyol, present is 1 to 20% by weight, 5 to 15% by weight or 8 to 12% by weight, based on the total weight of the isocyanate-reactive composition.

22. The laminated component according to any one of claims 1 to 21, wherein the polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g includes a polyol-initiated polyether polyol, such as an aliphatic polyol-initiated polyether polyol, which is different from the amine-initiated polyether polyol. For example, the hydroxyl value of the polyol-initiated polyether polyol is 200 to 500 mg KOH / g, 200 to 400 mg KOH / g, 200 to 300 mg KOH / g, 200 to 250 mg KOH / g, 230 to 250 mg KOH / g or 233 to 243 mg KOH / g, and / or the hydroxyl functionality is greater than 2 to 4, 2.5 to 3.5, or 3.

0.

23. The laminated component according to claim 22, wherein the aliphatic polyol-initiated polyether polyol is a reaction product of an H-functional initiator containing an aliphatic alcohol and an alkylene oxide. For example, the aliphatic alcohol includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, or a mixture of any two or more thereof.

24. The laminated component according to claim 23, wherein the aliphatic alcohol is present in an amount of greater than 50 wt%, at least 80 wt%, at least 90 wt% or 100 wt%, based on the total weight of the H-functional initiator of the polyether polyol used to prepare the polyol, for example, wherein the aliphatic alcohol initiator consists of glycerol and the alkylene oxide consists of propylene oxide.

25. The laminated component according to any one of claims 22 to 24, wherein the polyol-initiated polyether polyol is present in an amount of 10 to 30 wt%, 15 to 25 wt% or 15 to 20 wt%, based on the total weight of the isocyanate-reactive composition, and / or the polyol-initiated polyether polyol and the amine-initiated polyether polyol are present in a weight ratio of at least 1:1, 1:1 to 5:1, 1:1 to 2:1 or 1.5:1 to 2:

1.

26. The laminated component according to any one of claims 1 to 25, wherein the polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g includes an aromatic polyester polyol, for example, a reaction product of an aromatic diacid or aromatic anhydride with a diol or triol, for example, wherein the diol or triol includes ethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, trimethylolethane, trimethylolpropane, pentanediol, hexanediol, heptanediol, 1,3-dihydroxymethylcyclohexane and 1,4-dihydroxymethylcyclohexane, or a mixture of any two or more thereof, and / or the aromatic diacid or aromatic anhydride includes phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, or a mixture of any two or more thereof.

27. The laminated component according to claim 26, wherein the OH value of the aromatic polyester polyol is 150 to 410 mgKOH / g, 200 to 360 mg KOH / g or 300 to 360 mg KOH / g, and / or the functionality is 1.5 to 3 or 1.9 to 2.

5.

28. The laminated component according to claim 26 or claim 27, wherein the aromatic polyester polyol is present in an amount of 10 to 30 wt%, 15 to 25 wt% or 15 to 20 wt%, based on the total weight of the isocyanate-reactive composition, and / or the aromatic polyester polyol and the amine-initiated polyether polyol are present in a weight ratio of at least 1:1, 1:1 to 5:1, 1:1 to 2:1 or 1.5:1 to 2:1 in the isocyanate-reactive composition.

29. The laminated component according to any one of claims 1 to 28, wherein the diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.2 has a molecular weight of 62 to 200 g / mol and / or a hydroxyl functionality of 2.

0.

30. The laminated component according to any one of claims 1 to 29, wherein the diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.2 includes ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, butane-1,4-diol, butane-1,3-diol, butane-2,3-diol, pentane-1,5-diol, hexane-1,6-diol, 2,2-dimethylpropane-1,3-diol, 1,4-dihydroxycyclohexane, 1,4-bis(hydroxymethyl)cyclohexane, octane-1,8-diol, decane-1,10-diol, dodecane-1,12-diol, or a mixture of any two or more thereof.

31. The laminated component according to any one of claims 1 to 30, wherein the amount of the diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.2 is 5 to 30 wt%, 10 to 25 wt% or 15 to 25 wt%, based on the total weight of the isocyanate-reactive composition.

32. The laminated component according to any one of claims 1 to 30, wherein the diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.2 includes (i) a diol having a molecular weight of 62 to 110 g / mol, and (ii) a diol having a molecular weight of 111 to 200 g / mol, wherein the diol (i) and the diol (ii) are present in a weight ratio of at least 1:1, 1:1 to 5:1 or 1:1 to 2.

1.

33. The laminated component according to any one of claims 1 to 32, wherein the polyurethane outer layer is a non-foamed polyurethane outer layer.

34. The laminated component according to any one of claims 1 to 33, wherein the reaction mixture shows a gel time at the processing temperature of at least 15 seconds or at least 20 seconds and not more than 2 minutes, not more than 1 minute or not more than 30 seconds.

35. The laminated component according to any one of claims 1 to 34, wherein the polyurethane outer layer shows a Shore D hardness of at least 70 or at least 75 (measured according to ASTM D2240-15 (2021)), and / or a tensile strength of at least 5,000 psi (measured according to ASTM D638-22), and / or an elongation at break of at least 30% (measured according to ASTM D638-22), and / or a flexural modulus of at least 225,000 psi (measured according to ASTM D 790-17), and / or a heat deflection temperature of at least 160°F @ 66 psi (measured according to ASTM D648-18).

36. The laminated component according to any one of claims 1 to 35, wherein the laminated component further includes a second polyurethane outer layer, such as a polyurethane outer layer having a Class A surface.

37. The laminated component according to claim 36, wherein the second polyurethane outer layer comprises a cured reaction product of a reaction mixture, the reaction mixture comprising: (1) a polyisocyanate; (2) a polyether polyol having a molecular weight of 800 Da to 25,000 Da and a functionality of 2 to 8; and (3) 0.5 to 15% by weight of a fatty acid ester based on the total weight of the reaction mixture, the fatty acid ester having an isocyanate-reactive functionality of at least 1 and a hydroxyl value of 10 to 20 mg KOH / g.

38. The laminated component according to any one of claims 1 to 37, wherein the isocyanate index of the reaction mixture is 70 to 130, 80 to 120 or 90 to 110.

39. An automotive roof, hood, fender, door or floor module or load floor, comprising the laminated component according to any one of claims 1 to 38.

40. A method for preparing a laminated component, comprising: (a) inserting a sandwich structure into a mold cavity, wherein the sandwich structure comprises: (1) a core, and (2) fiber layers disposed on each side of the core, each fiber layer being impregnated with a polyurethane resin; (b) closing the mold; (c) injecting a reaction mixture for forming polyurethane into the cavity by a RIM process; (d) reacting the reaction mixture in the closed mold to form a polyurethane outer layer deposited on at least a portion of at least one polyurethane-impregnated fiber layer; (e) opening the mold; and (f) removing the laminated component from the opened mold, wherein the reaction mixture for forming polyurethane comprises: (1) a polyisocyanate; and (2) an isocyanate-reactive composition having a total hydroxyl value of 300 to 700 mg KOH / g, wherein the isocyanate-reactive composition comprises: (i) a polyether polyol having a hydroxyl functionality of 2 to 4 and a hydroxyl value of 20 to 60 mg KOH / g, (ii) a polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g, which comprises an amine-initiated polyether polyol, and (iii) a diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.

2.

41. The method according to claim 40, wherein the isocyanate index of the reaction mixture for forming polyurethane is 70 to 130, 80 to 120 or 90 to 110.

42. The method according to claim 40 or 41, wherein the initial temperature of the reaction mixture introduced into the mold cavity is in the range of 20 to 80 °C or 30 to 70 °C and / or the temperature in the mold cavity is in the range of 30 to 130 °C or 40 to 80 °C.

43. The method according to any one of claims 40 to 42, wherein the molded laminated component is removed from the mold after an in-mold dwell time of 5 to 180 seconds.

44. The method according to any one of claims 40 to 43, wherein the core is made of paper, such as multi-layer paper, cardboard or resin-impregnated paper.

45. The method according to any one of claims 40 to 44, wherein the core comprises a cavity, for example wherein the core has a corrugated, angular, honeycomb or foamed profile.

46. The method according to any one of claims 40 to 45, wherein the core has a thickness of 5 to 50 millimeters and / or a density of 10 to 1000 kg / m 3 .

47. The method according to any one of claims 40 to 46, wherein the fiber layer comprises a glass fiber mat, a chopped glass fiber strand mat, a random glass fiber layer, a glass fiber fabric, cut or shredded glass fibers or mineral fibers, a natural fiber mat, a knitted fabric, cut natural fibers, non-woven fabrics and knitted fabrics based on polymer, carbon or aramid fibers, or a mixture thereof.

48. The method according to any one of claims 40 to 47, wherein the thickness of the fibrous layer is from 0.1 to 2 millimeters and / or the basis weight of the fibrous layer is from 225 to 1200 g / m 2 .

49. The method according to any one of claims 40 to 48, wherein the polyurethane resin impregnating the fiber layer comprises the reaction product of a reaction mixture comprising: (1) a polyisocyanate; (2) a polyol component having an average OH value of 300 to 700, and in some embodiments, the polyol component comprises at least one short-chain polyol and one long-chain polyol, and the initial polyol has a hydroxyl functionality of 2 to 6; (3) water; (4) an activator; (5) a stabilizer; and optionally, (6) other auxiliary materials, release agents and additives.

50. The method according to any one of claims 40 to 49, wherein the weight per unit area of the cured polyurethane resin impregnating the fiber layer is 400 to 1200 g / m 2 .

51. The method according to any one of claims 40 to 50, wherein the polyisocyanate comprises a methylene-bridged polyphenyl polyisocyanate and / or a prepolymer of a methylene-bridged polyphenyl polyisocyanate, having an average functionality of 1.8 to 3.5 isocyanate moieties per molecule, for example 2.0 to 3.1 isocyanate moieties, and an NCO content of 20 to 32% by weight.

52. The method according to any one of claims 40 to 51, wherein the total hydroxyl value of the isocyanate-reactive composition is 300 to 500 mg KOH / g or 300 to 400 mg KOH / g.

53. The method according to any one of claims 40 to 52, wherein the polyether polyol having a hydroxyl functionality of 2 to 4 and a hydroxyl value of 20 to 60 mg KOH / g has a hydroxyl functionality of 2.5 to 3.5 or 2.8 to 3.2 and / or a hydroxyl value of 20 to 50 mg KOH / g or 25 to 40 mg KOH / g.

54. The method according to any one of claims 40 to 53, wherein the polyether polyol having a hydroxyl functionality of 2 to 4 and a hydroxyl value of 20 to 60 mg KOH / g is a reaction product of an alkylene oxide such as ethylene oxide and / or propylene oxide with an initiator, the initiator comprising water, 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose, castor oil, modified soybean oil, or a mixture of any two or more thereof.

55. The method according to any one of claims 40 to 54, wherein the propylene oxide content of the polyether polyol having a functionality of 2 to 4 and an OH value of 20 to 60 mg KOH / g is 70 to 90% by weight or 75 to 85% by weight, and the ethylene oxide content is 10 to 30% by weight or 15 to 25% by weight, based on the total weight of the alkylene oxides used for preparing the polyether polyol.

56. The method according to any one of claims 40 to 55, wherein the amount of the polyether polyol having a functionality of 2 to 4 and an OH value of 20 to 60 mg KOH / g is at least 30% by weight, 30 to 50% by weight or 30 to 40% by weight, based on the total weight of the isocyanate-reactive composition used for preparing the polyurethane outer layer.

57. The method according to any one of claims 40 to 56, wherein the hydroxyl functionality of the polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g is 2 to 4 and / or the hydroxyl value is 300 to 400 mg KOH / g.

58. The method according to any one of claims 40 to 57, wherein the amount of the polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g is at least 20% by weight, 20 to 60% by weight, 30 to 50% by weight or 40 to 50% by weight, based on the total weight of the isocyanate-reactive composition.

59. The method according to any one of claims 40 to 58, wherein the polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g includes amine-initiated polyether polyols, such as aromatic amine-initiated polyether polyols.

60. The method according to claim 59, wherein the aromatic amine-initiated polyether polyol is a reaction product of an alkylene oxide and an H-functional initiator containing an aromatic amine, and the aromatic amine is, for example, 2,3-TDA and 3,4-TDA.

61. The method according to claim 60, wherein the amount of the aromatic amine is greater than 50% by weight, at least 80% by weight, at least 90% by weight or 100% by weight, based on the total weight of the H-functional initiator used for preparing the aromatic amine-initiated polyether polyol.

62. The method according to claim 60 or claim 61, wherein the amount of propylene oxide is greater than 50% by weight, at least 60% by weight, 60 to 90% by weight, 60 to 80% by weight or 60 to 70% by weight, based on the total weight of the alkylene oxides used for preparing the aromatic amine-initiated polyether polyol, and / or the amount of ethylene oxide is not more than 50% by weight, not more than 40% by weight, 10 to 40% by weight, 20 to 40% by weight or 30 to 40% by weight, based on the total weight of the alkylene oxides used for preparing the aromatic amine-initiated polyether polyol.

63. The method according to any one of claims 59 to 62, wherein the amine-initiated polyether polyol, such as an aromatic amine-initiated polyether polyol, is present in an amount of 1 to 20% by weight, 5 to 15% by weight, or 8 to 12% by weight, based on the total weight of the isocyanate-reactive composition.

64. The method according to any one of claims 40 to 63, wherein the polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g includes a polyol-initiated polyether polyol, such as an aliphatic polyol-initiated polyether polyol, which is different from the amine-initiated polyether polyol, for example, wherein the hydroxyl value of the polyol-initiated polyether polyol is 200 to 500 mg KOH / g, 200 to 400 mg KOH / g, 200 to 300 mg KOH / g, 200 to 250 mg KOH / g, 230 to 250 mg KOH / g, or 233 to 243 mg KOH / g, and / or the hydroxyl functionality is greater than 2 to 4, 2.5 to 3.5, or 3.

0.

65. The method according to claim 64, wherein the aliphatic polyol-initiated polyether polyol is a reaction product of an H-functional initiator containing an aliphatic alcohol and an alkylene oxide, for example, wherein the aliphatic alcohol includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, or a mixture of any two or more thereof.

66. The method according to claim 65, wherein the aliphatic alcohol is present in an amount greater than 50% by weight, at least 80% by weight, at least 90% by weight, or 100% by weight, based on the total weight of the H-functional initiator used to prepare the polyol-initiated polyether polyol, for example, wherein the aliphatic alcohol initiator consists of glycerol and the alkylene oxide consists of propylene oxide.

67. The method according to any one of claims 64 to 66, wherein the polyol-initiated polyether polyol is present in an amount of 10 to 30% by weight, 15 to 25% by weight, or 15 to 20% by weight, based on the total weight of the isocyanate-reactive composition, and / or the polyol-initiated polyether polyol and the amine-initiated polyether polyol are present in a weight ratio of at least 1:1, 1:1 to 5:1, 1:1 to 2:1, or 1.5:1 to 2:

1.

68. The method according to any one of claims 40 to 67, wherein the polyol having a hydroxyl functionality of 1.5 to 5.0 and a hydroxyl value of 200 to 600 mg KOH / g includes an aromatic polyester polyol, such as a reaction product of an aromatic diacid or aromatic anhydride with a diol or triol, for example, wherein the diol or triol includes ethylene glycol, propylene glycol, butylene glycol, 1,3 - butylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, trimethylolethane, trimethylolpropane, pentanediol, hexanediol, heptanediol, 1,3 - bis(hydroxymethyl)cyclohexane, and 1,4 - bis(hydroxymethyl)cyclohexane, or a mixture of any two or more thereof, and / or the aromatic diacid or aromatic anhydride includes phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, or a mixture of any two or more thereof.

69. The method according to claim 68, wherein the OH value of the aromatic polyester polyol is 150 to 410 mg KOH / g, 200 to 360 mg KOH / g, or 300 to 360 mg KOH / g and / or the functionality is 1.5 to 3 or 1.9 to 2.

5.

70. The method according to claim 68 or claim 69, wherein the amount of the aromatic polyester polyol is 10 to 30% by weight, 15 to 25% by weight, or 15 to 20% by weight, based on the total weight of the isocyanate - reactive composition, and / or the aromatic polyester polyol and the amine - initiated polyether polyol are present in the isocyanate - reactive composition in a weight ratio of at least 1:1, 1:1 to 5:1, 1:1 to 2:1, or 1.5:1 to 2:

1.

71. The method according to any one of claims 40 to 70, wherein the diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.2 has a molecular weight of 62 to 200 g / mol and / or a hydroxyl functionality of 2.

0.

72. The method according to any one of claims 40 to 71, wherein the diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.2 includes ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, but - 1,4 - diol, but - 1,3 - diol, but - 2,3 - diol, pent - 1,5 - diol, hex - 1,6 - diol, 2,2 - dimethylprop - 1,3 - diol, 1,4 - dihydroxycyclohexane, 1,4 - bis(hydroxymethyl)cyclohexane, oct - 1,8 - diol, dec - 1,10 - diol, dodecane - 1,12 - diol, or a mixture of any two or more thereof.

73. The method according to any one of claims 40 to 72, wherein the amount of the diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.2 is 5 to 30% by weight, 10 to 25% by weight, or 15 to 25% by weight, based on the total weight of the isocyanate - reactive composition.

74. The method according to any one of claims 40 to 73, wherein the diol having a molecular weight of 62 to 399 g / mol and a hydroxyl functionality of 1.8 to 2.2, in certain embodiments, comprises (i) a diol having a molecular weight of 62 to 110 g / mol, and (ii) a diol having a molecular weight of 111 to 200 g / mol, wherein the diol (i) and the diol (ii) are present in a weight ratio of at least 1:1, 1:1 to 5:1 or 1:1 to 2.

1.

75. The method according to any one of claims 40 to 74, wherein the polyurethane outer layer is a non-foamed polyurethane outer layer.

76. The method according to any one of claims 40 to 75, wherein the reaction mixture exhibits a gel time at the processing temperature of at least 15 seconds or at least 20 seconds and not exceeding 2 minutes, not exceeding 1 minute or not exceeding 30 seconds.

77. The method according to any one of claims 40 to 76, wherein the polyurethane outer layer exhibits a Shore D hardness of at least 70 or at least 75 (measured according to ASTM D2240-15(2021)), and / or a tensile strength of at least 5,000 psi (measured according to ASTM D638-22), and / or an elongation at break of at least 30% (measured according to ASTM D638-22), and / or a flexural modulus of at least 225,000 psi (measured according to ASTM D 790-17), and / or a heat deflection temperature of at least 160°F @ 66 psi (according to ASTM D648-18).

78. The method according to any one of claims 40 to 77, wherein the laminated component further comprises a second polyurethane outer layer, such as a polyurethane outer layer having a Class A surface.

79. The method according to claim 78, wherein the second polyurethane outer layer comprises the cured reaction product of a reaction mixture comprising: (1) a polyisocyanate; (2) a polyether polyol having a molecular weight of 800 Da to 25,000 Da and a functionality of 2 to 8; and (3) 0.5 to 15% by weight, based on the total weight of the reaction mixture, of a fatty acid ester having an isocyanate-reactive functionality of at least 1 and a hydroxyl value of 10 to 20 mg KOH / g.

80. An automotive roof, hood, fender, door or floor module, or load floor, comprising a laminated component made by the method according to any one of claims 40 to 79.