阅读说明：本技术 包含防滑和防水外层的层压部件及其制备方法 (Laminate part comprising an outer anti-slip and waterproof layer and method for the production thereof ) 是由 M·W·莱斯科 于 2020-03-23 设计创作，主要内容包括：本发明描述了层压部件,其包括芯、布置在所述芯的每一侧上并浸渍有聚氨酯树脂的纤维层和至少部分地涂覆聚氨酯浸渍的纤维层中的至少一层的外层,其中所述外层为反应混合物的固化反应产物,所述反应混合物包括：(1)多异氰酸酯,(2)分子量为800Da至25,000Da且官能度为2至8的聚醚多元醇,和(3)具有异氰酸酯反应性官能度的脂肪酸酯。本发明还描述了制备所述层压部件的方法。(The present invention describes a laminate part comprising a core, a fibre layer arranged on each side of the core and impregnated with a polyurethane resin and an outer layer at least partially coating at least one of the polyurethane impregnated fibre layers, wherein the outer layer is a cured reaction product of a reaction mixture comprising: (1) a polyisocyanate, (2) a polyether polyol having a molecular weight of 800Da to 25,000Da and a functionality of 2 to 8, and (3) a fatty acid ester having isocyanate-reactive functionality. Methods of making the laminated parts are also described.)

1. A laminate part comprising:

(a) a core;

(b) a fiber layer disposed on each side of the core and impregnated with a polyurethane resin, and

(c) an outer layer at least partially coating at least one of the polyurethane impregnated fibrous layers,

wherein the outer layer is a cured reaction product of a reaction mixture comprising: (1) a polyisocyanate; (2) a polyether polyol having a molecular weight of 800Da to 25,000Da and a functionality of 2 to 8; and (3) 0.5 to 15 weight percent, based on the total weight of the reaction mixture, of a fatty acid ester having an isocyanate-reactive functionality of at least 1.

2. The laminate component of claim 1, wherein the core is comprised of: metals, such as aluminum, magnesium, or alloys thereof; reinforced, unreinforced, filled or unfilled plastics, such as polyamides, polyesters, polycarbonates, polypropylenes, polystyrenes, ABS, polyamideimides or mixtures thereof; natural materials such as wood, flax, sisal, jute, hemp, or mixtures thereof; and/or paper, such as multi-ply paper, paperboard, resin impregnated paper, or mixtures thereof.

3. The laminate component of claim 1 or claim 2, wherein the core comprises a cavity, such as an angular or circular channel, hole, or bubble.

4. A laminated part according to any one of claims 1 to 3, wherein the core has a corrugated, angular, honeycomb or foam-like profile, such as corrugated metal or corrugated cardboard.

5. The laminate part according to any one of claims 1 to 4, wherein the core has a thickness of 5 to 50 mm and/or a density of 10 to 1000kg/m³。

6. The laminate component of any one of claims 1 to 5, wherein the fiber layer comprises glass fiber mats, chopped glass strand mats, random glass fiber layers, glass fiber fabrics, cut or milled glass or mineral fibers, natural fiber mats, knitted fabrics, cut natural fibers or fiber mats, polymer-based nonwovens and knitted fabrics, carbon fibers or aramid fibers, or mixtures thereof, for example wherein natural fibers comprise flax, sisal, jute, hemp, or mixtures thereof.

7. The laminate component according to any one of claims 1 to 6, wherein the thickness of the fibre layer is 0.1 to 2 mm and/or the weight of the fibre layer per unit area is 225 to 1200g/m²。

8. The laminate component of any one of claims 1 to 7, wherein the polyurethane resin partially or completely fills the cavity of the core.

9. The laminate component of any one of claims 1 to 8, wherein the polyurethane is formed from a one or more component polyurethane forming system and is foamed or non-foamed.

10. The laminate component of any one of claims 1 to 9, wherein the polyurethane is a polyurethane resin comprising a reaction product of a reaction mixture comprising: (1) at least one polyisocyanate; (2) at least one polyol component having an average OH number of from 300 to 700, the polyol component comprising at least one short chain polyol and one long chain polyol, the initial polyol having a functionality of from 2 to 6; (3) water; (4) an activator; (5) a stabilizer; and optionally, (6) other auxiliary materials, release agents and additives, for example wherein the polyol component comprises a polyester polyol and/or polyether polyol, the polyisocyanate comprises a polymeric isocyanate of the diphenylmethane diisocyanate series (pMDI type), a prepolymer thereof or crude MDI, water is used in an amount of from 0.1 to 3.0 parts, for example from 0.3 to 2.0 parts, per 100 parts of the polyol formulation, the activator comprises an amine or metal salt, and/or the stabilizer comprises a polyether siloxane, for example a water-soluble polyether siloxane.

11. The laminate part according to any one of claims 1 to 10, wherein the weight of polyurethane per unit area is 400 to 1200g/m²。

12. The laminate part of any one of claims 1 to 11, wherein the polyisocyanate comprises an aliphatic, cycloaliphatic, araliphatic, aromatic and/or heterocyclic polyisocyanate, such as of formula q (nco)_nWherein n is 2, 3 or 4, and Q is an aliphatic hydrocarbon group having 2 to 18, such as 6 to 10 carbon atoms, an alicyclic hydrocarbon group having 4 to 15, such as 5 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 15, such as 6 to 13 carbon atoms, orAraliphatic hydrocarbon radicals having 8 to 15, for example 8 to 13, carbon atoms.

13. The laminate part of any one of claims 1 to 12, wherein the polyisocyanate comprises 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-Durene Diisocyanate (DDI), 4 ' -stilbene diisocyanate, 3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate (TODI), 2, 4-and 2, 6-Toluene Diisocyanate (TDI) and any mixtures of these isomers, diphenylmethane-2, 4 ' -diisocyanate and/or diphenylmethane-4, 4 ' -diisocyanate (MDI), naphthylene-1, 5-diisocyanate, triphenylmethane-4, 4', 4 "-triisocyanate, polyphenyl-polymethylene polyisocyanates (as obtained by condensation of aniline with formaldehyde and subsequent phosgenation), m-and p-isocyanatophenylsulfonyl isocyanates, perchloroaryl polyisocyanates, polyisocyanates having carbodiimide groups, norbornane diisocyanates, polyisocyanates having allophanate groups, polyisocyanates having isocyanurate groups, polyisocyanates having urethane groups, polyisocyanates having acylated urea groups, polyisocyanates having biuret groups, polyisocyanates prepared by telomerization, polyisocyanates having ester groups, reaction products of the above isocyanates with acetals, and polyisocyanates containing polymeric fatty acid esters, or a mixture of any two or more of the above polyisocyanates.

14. The laminate part of any one of claims 1 to 13, wherein the polyisocyanate comprises a prepolymer having isocyanate groups prepared by: the polyols and/or chain extenders and/or crosslinkers are reacted with at least one aromatic diisocyanate selected from the group consisting of TDI, MDI, TODI, DIBDI, NDI, DDI, for example 4, 4' -MDI, to give polyaddition products having urethane groups and isocyanate groups with an NCO content of 6 to 25% by weight.

15. The laminate part of any one of claims 1 to 14, 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, such as 2.0 to 3.1, isocyanate moieties per molecule and an NCO content of 20 to 32 weight percent.

16. The laminate part of any one of claims 1 to 15, wherein the polyether polyol has a molecular weight of 800 to 14,000Da or 1,000 to 8,000Da, and/or a functionality of 2.4 to 8 or 2.5 to 3.5.

17. The laminate part of any one of claims 1-16, wherein the polyether polyol comprises polyoxyethylene glycol, triol, tetraol, and higher functionality polyoxyethylene polyols, polyoxypropylene glycol, triol, tetraol, and higher functionality polyoxyethylene polyols, or a mixture of any two or more thereof, for example wherein the polyether polyol is prepared from an initiator or initiator comprising ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, ethylenediamine, and toluene diamine, or a mixture of any two or more thereof.

18. The laminate part of any one of claims 1 to 17, wherein the reaction mixture comprises a low molecular difunctional chain extender, a trifunctional or tetrafunctional crosslinker, or a mixture of chain extender and crosslinker, for example wherein the chain extender comprises an alkanediol or dialkylene glycol, and the crosslinker comprises a 3-or 4-valent alcohol and/or oligomeric polyalkylene polyol having a functionality of 3 to 4 and a molecular weight of < 750g/mol, for example 18 to 400g/mol or 60 to 300 g/mol.

19. The laminate part of clause 18, wherein the chain extender and/or cross-linker is present in an amount of no greater than 50 weight percent, such as no greater than 20 weight percent, such as from 1 to 50 weight percent or from 2 to 20 weight percent, based on the total weight of isocyanate-reactive ingredients in the reaction mixture.

20. The laminate part of any one of claims 1 to 19, wherein the fatty acid ester is present in an amount of 0.5 to 5 wt.%, based on the total weight of the reaction mixture.

21. The laminate component of any one of claims 1-20, wherein the fatty acid ester comprises an ester reaction product of a fatty acid having from 5 to 32 carbon atoms, such as from 12 to 22 carbon atoms, and a mono-or polyhydric alcohol having from 2 to 30 carbon atoms, such as from 2 to 22 carbon atoms, for example wherein the fatty acid comprises a saturated fatty acid, such as hexanoic acid, octanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, stearic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and/or melissic acid, and/or an unsaturated fatty acid, such as oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, brassidic acid, erucic acid, and/or ricinoleic acid, and mixtures of any two or more thereof, and/or wherein the alcohol comprises a mono-alcohol, such as propanol, isopropanol, ricinoleic acid, and mixtures of any two or more thereof, Isopropanol, butanol, octanol (capryl alcohol), octanol (caprylyl alcohol), lauryl alcohol, myristyl alcohol, stearyl alcohol, and behenyl alcohol, and/or polyols such as ethylene glycol, propylene glycol, butylene glycol, glycerol, trimethylolpropane, pentaerythritol, isotridecanol, and neopentyl glycol, and mixtures of any two or more thereof.

22. The laminate component of any one of claims 1 to 21, wherein the fatty acid ester has an isocyanate-reactive functionality, such as a hydroxyl functionality, of from 1 to 2 and/or a hydroxyl number of at least 10mg KOH/g, such as from 10 to 50mg KOH/g or from 10 to 20mg KOH/g.

23. The laminate part of any one of claims 1 to 22, wherein the laminate part is a vehicle roof, hood, tail, door or floor module, or load-bearing floor.

24. A method of making a laminated part, the method comprising:

(a) inserting a sandwich structure into a mold having a cavity therein, wherein at least a portion of the cavity defines a mold cavity surface having a non-reactive, silicon-free release agent deposited thereon, the sandwich structure comprising: (1) a core, and (2) fiber layers disposed on each side of the core, each fiber layer impregnated with a polyurethane resin;

(b) closing the mold;

(c) injecting the reaction mixture into the cavity by a RIM process;

(d) reacting the reaction mixture in a closed mold to form an outer layer at least partially coating at least one of the polyurethane impregnated fiber layers;

(e) opening the mold; and

(f) the laminated part is removed from the open mould,

wherein the reaction mixture comprises: (1) a polyisocyanate; (2) a polyether polyol having a molecular weight of from 1,800Da to 12,000Da and a functionality of at least 2; and (3) 0.5 to 15 weight percent, based on the total weight of the reaction mixture, of a fatty acid ester having an isocyanate-reactive functionality of at least 1.

25. The method of claim 24, wherein the non-reactive, silicon-free release agent comprises a non-transfer wax.

26. The method of claim 24 or claim 25, wherein the core is comprised of: metals, such as aluminum, magnesium, or alloys thereof; reinforced, unreinforced, filled or unfilled plastics, such as polyamides, polyesters, polycarbonates, polypropylenes, polystyrenes, ABS, Polyamideimides (PAI) or mixtures thereof; natural materials such as wood, flax, sisal, jute, hemp, or mixtures thereof; and/or paper, such as multi-ply paper, paperboard, resin impregnated paper, or mixtures thereof.

27. The method of any one of claims 24 to 26, wherein the core comprises a cavity, such as an angular or circular channel, a hole, or a bubble.

28. A method according to any one of claims 24 to 27, wherein the core has a corrugated, angular, honeycomb or foam-like profile, such as corrugated metal or corrugated cardboard.

29. The method of any one of claims 24 to 28, wherein the core has a thickness of 5 to 50 millimeters and/or a density of 10 to 1000kg/m³。

30. The method of any one of claims 24 to 29, wherein the fiber layer comprises glass fiber mats, chopped glass strand mats, random glass fiber layers, glass fiber fabrics, cut or milled glass or mineral fibers, natural fiber mats, knitted fabrics, cut natural fibers or fiber mats, polymer-based nonwovens and knitted fabrics, carbon fibers or aramid fibers, or mixtures thereof, for example wherein natural fibers comprise flax, sisal, jute, hemp, or mixtures thereof.

31. The method according to any one of claims 24 to 30, wherein the thickness of the fibre layer is 0.1 to 2 millimetres and/or the weight of the fibre layer per unit area is 225 to 1200g/m²。

32. The method of any one of claims 24 to 31, wherein the polyurethane resin partially or completely fills the cavity of the core.

33. The method of any one of claims 24 to 32, wherein the polyurethane is formed from a one or more component polyurethane forming system and is foamed or non-foamed.

34. The method of any one of claims 24 to 33, wherein the polyurethane is a polyurethane resin comprising a reaction product of a reaction mixture comprising: (1) at least one polyisocyanate; (2) at least one polyol component having an average OH number of from 300 to 700, the polyol component comprising at least one short chain polyol and one long chain polyol, the initial polyol having a functionality of from 2 to 6; (3) water; (4) an activator; (5) a stabilizer; and optionally, (6) other auxiliary materials, release agents and additives, for example wherein the polyol component comprises a polyester polyol and/or polyether polyol, the polyisocyanate comprises a polymeric isocyanate of the diphenylmethane diisocyanate series (pMDI type), a prepolymer thereof or crude MDI, water is used in an amount of from 0.1 to 3.0 parts, for example from 0.3 to 2.0 parts, per 100 parts of the polyol formulation, the activator comprises an amine or metal salt, and/or the stabilizer comprises a polyether siloxane, for example a water-soluble polyether siloxane.

35. The method of any one of claims 24 through 34, wherein the weight per unit area of polyurethane is from 400 to 1200g/m²。

36. The method of any one of claims 24-35, wherein the polyisocyanate comprises an aliphatic, cycloaliphatic, araliphatic, aromatic and/or heterocyclic polyisocyanate, such as of formula q (nco)_nWherein n is 2, 3 or 4, and Q is an aliphatic hydrocarbon group having 2 to 18, for example 6 to 10 carbon atoms, a cycloaliphatic hydrocarbon group having 4 to 15, for example 5 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 15, for example 6 to 13 carbon atoms, or an araliphatic hydrocarbon group having 8 to 15, for example 8 to 13 carbon atoms.

37. The method of any one of claims 24 to 36, wherein the polyisocyanate comprises 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-Durene Diisocyanate (DDI), 4 ' -stilbene diisocyanate, 3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate (TODI), 2, 4-and 2, 6-Toluene Diisocyanate (TDI) and any mixtures of these isomers, diphenylmethane-2, 4 ' -diisocyanate and/or diphenylmethane-4, 4 ' -diisocyanate (MDI), naphthylene-1, 5-diisocyanate, triphenylmethane-4, 4', 4 "-triisocyanate, polyphenyl-polymethylene polyisocyanates (as obtained by condensation of aniline with formaldehyde and subsequent phosgenation), m-and p-isocyanatophenylsulfonyl isocyanates, perchloroaryl polyisocyanates, polyisocyanates having carbodiimide groups, norbornane diisocyanates, polyisocyanates having allophanate groups, polyisocyanates having isocyanurate groups, polyisocyanates having urethane groups, polyisocyanates having acylated urea groups, polyisocyanates having biuret groups, polyisocyanates prepared by telomerization, polyisocyanates having ester groups, reaction products of the above isocyanates with acetals, and polyisocyanates containing polymeric fatty acid esters, or a mixture of any two or more of the above polyisocyanates.

38. The method of any one of claims 24 through 37, wherein the polyisocyanate comprises a prepolymer having isocyanate groups prepared by: the polyols and/or chain extenders and/or crosslinkers are reacted with at least one aromatic diisocyanate selected from the group consisting of TDI, MDI, TODI, DIBDI, NDI, DDI, for example 4, 4' -MDI, to give polyaddition products having urethane groups and isocyanate groups and an NCO content of 6 to 25% by weight.

39. The process of any one of claims 24 to 38, 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, such as 2.0 to 3.1, isocyanate moieties per molecule and an NCO content of 20 to 32 weight percent.

40. The method of any one of claims 24 to 39, wherein the polyether polyol has a molecular weight of from 800 to 14,000Da or from 1,000 to 8,000Da, and/or a functionality of from 2.4 to 8 or from 2.5 to 3.5.

41. The method of any one of claims 24 to 40, wherein the polyether polyol comprises a polyoxyethylene glycol, triol, tetraol, and higher functionality polyoxyethylene polyols, a polyoxypropylene glycol, triol, tetraol, and higher functionality polyoxyethylene polyols, or a mixture of any two or more thereof, for example wherein the polyether polyol is prepared from a starter or initiator comprising ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, ethylenediamine, and toluenediamine, or a mixture of any two or more thereof.

42. The process of any one of claims 24 to 41, wherein the reaction mixture comprises a low molecular difunctional chain extender, a trifunctional or tetrafunctional crosslinker, or a mixture of chain extender and crosslinker, for example wherein the chain extender comprises an alkanediol or dialkylene glycol and the crosslinker comprises a 3-or 4-valent alcohol and/or an oligomeric polyalkylene polyol having a functionality of 3 to 4 and a molecular weight of < 750g/mol, for example 18 to 400g/mol or 60 to 300 g/mol.

43. A process according to claim 42, wherein the chain extender and/or cross-linker is present in an amount of no more than 50 wt%, such as no more than 20 wt%, for example from 1 to 50 wt% or from 2 to 20 wt%, based on the total weight of isocyanate-reactive ingredients in the reaction mixture.

44. The process of any one of claims 24 to 43, wherein the fatty acid ester is present in an amount of from 0.5 to 5 weight percent, based on the total weight of the reaction mixture.

45. The method of any one of claims 24 to 44, wherein the fatty acid ester comprises an ester reaction product of a fatty acid having from 5 to 32 carbon atoms, such as from 12 to 22 carbon atoms, and a monohydric or polyhydric alcohol having from 2 to 30 carbon atoms, such as from 2 to 22 carbon atoms, for example wherein the fatty acid comprises a saturated fatty acid, such as caproic acid, caprylic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, stearic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid and/or melissic acid, and/or an unsaturated fatty acid, such as oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, brassidic acid, erucic acid and/or ricinoleic acid, and mixtures of any two or more thereof, and/or wherein the alcohol comprises a monohydric alcohol, such as propanol, isopropanol, an ester reaction product of a fatty acid, such as from 12 to 22 carbon atoms, for example, Butanol, octanol (caprylyl alcohol), lauryl alcohol, myristyl alcohol, stearyl alcohol, and behenyl alcohol, and/or polyols such as ethylene glycol, propylene glycol, butylene glycol, glycerol, trimethylolpropane, pentaerythritol, isotridecanol, and neopentyl glycol, and mixtures of any two or more thereof.

46. The method of any one of claims 24 to 45, wherein the fatty acid ester has an isocyanate-reactive (e.g. hydroxyl) functionality of from 1 to 2 and/or a hydroxyl number of at least 10mg KOH/g, such as from 10 to 50mg KOH/g or from 10 to 20mg KOH/g.

47. A method according to any one of claims 24 to 46, wherein the laminate component is a roof, hood, tail, door or floor module, or load-bearing floor.

Technical Field

The present description relates generally to laminate parts comprising outer layers and a polyurethane sandwich material, wherein at least one of the outer layers is slip-resistant and waterproof, and to a method of making the parts, comprising using the parts as load floor of an automobile.

Background

Fiber reinforced sandwich panels are used to make various laminated automotive parts, such as load-bearing floor panels. These parts are sometimes prepared by arranging a layer of fibers on each side of the honeycomb core and then impregnating the fiber layers with a polyurethane resin to bond the layers together. The part is then molded under heat before the polyurethane resin cures. An outer layer having a class a surface quality may be placed on one of the polyurethane impregnated fiber layers while a decorative layer (e.g., a fabric layer) is placed on the other layer.

However, in some applications, it may be desirable to replace the fabric layer with a water-repellent and uv-resistant coating having a class a surface quality. However, in order to be practical, particularly for load-bearing floor applications, the coating must exhibit good slip resistance. Otherwise, if the coating is slippery, objects placed on the load floor tend to slide within the vehicle, which is undesirable.

However, the manufacturing process used to produce the laminated parts is not conducive to obtaining such non-slip coatings. This is because the inner surface of the mold used in the press forming operation must be coated with a release agent in order to enable the laminated part to be released from the mold without damaging the part. However, silicone-based mold release agents used in these applications have heretofore tended to transfer to the part, thereby smoothing its outer surface and creating a "striped" appearance.

It is therefore highly desirable to provide a laminate component suitable for use as an automotive load-bearing floor, having a water-resistant and non-slip outer coating and having a class a surface quality. There is also a great need for a process for making such laminated parts without the use of silicone-based release agents.

The present invention has been made in view of the above circumstances.

Disclosure of Invention

In certain aspects, the present disclosure relates to laminated components. These laminated parts comprise: (a) a core; (b) a fiber layer disposed on each side of the core and impregnated with a polyurethane resin; and (c) an outer layer at least partially coating at least one of the polyurethane impregnated fibrous layers. The outer layer is a cured reaction product of a reaction mixture comprising: (1) a polyisocyanate; (2) a polyether polyol having a molecular weight of 800Da to 25,000Da and a functionality of 2 to 8; and (3) 0.5 to 15 weight percent, based on the total weight of the reaction mixture, of a fatty acid ester having an isocyanate-reactive functionality of at least 1.

In other aspects, the present disclosure relates to methods of making laminated parts. The method comprises the following steps: (a) inserting a sandwich structure into a mold having a cavity therein, wherein at least a portion of the cavity defines a mold cavity surface having a non-reactive, silicon-free release agent deposited thereon, the sandwich structure comprising: (1) a core, and (2) fiber layers disposed on each side of the core, each fiber layer impregnated with a polyurethane resin; (b) closing the mold; (c) injecting the reaction mixture into the cavity by a RIM process; (d) reacting the reaction mixture in a closed mold to form an outer layer at least partially coating at least one of the polyurethane impregnated fiber layers; (e) opening the mold; and (f) removing the laminated part from the open mold. The reaction mixture used in the process comprises: (1) a polyisocyanate; (2) a polyether polyol having a molecular weight of from 1,800Da to 12,000Da and a functionality of at least 2; and (3) 0.5 to 15 weight percent, based on the total weight of the reaction mixture, of a fatty acid ester having an isocyanate-reactive functionality of at least 1.

Detailed Description

Various embodiments are described and illustrated in this specification to provide a thorough understanding of the structure, function, performance, and use of the disclosed invention. It should be understood that the various embodiments described and illustrated in this specification are non-limiting and non-exhaustive. Accordingly, the invention is not limited by the description 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 included within the scope of this specification. Thus, the claims may be amended to recite any features or characteristics explicitly or inherently described in, or otherwise explicitly or inherently supported by, the present specification. Further, the applicant reserves the right to amend the claims to expressly disclaim features or characteristics that may be present in the prior art. Accordingly, any such modifications comply with the requirements of 35u.s.c. § 112 and 35u.s.c. § 132 (a). The various embodiments disclosed and described in this specification can include, consist of, or consist essentially of the features and characteristics described herein in various ways.

Unless otherwise indicated, any patent, publication, or other disclosure material, identified herein, is incorporated by reference in its entirety into this specification, but only to the extent that the incorporated material does not conflict with existing definitions, statements, or other disclosure material set forth in this specification. Accordingly, and to the extent necessary, the explicit disclosure set forth in this specification supersedes any conflicting material incorporated herein by reference. Any material, or portion thereof, that is said to be incorporated by reference herein, but which conflicts with existing definitions, statements, or other disclosure material set forth herein is only incorporated to the extent that no conflict arises between that incorporated material and the existing disclosure material. Applicants reserve the right to modify any subject matter or portion thereof from this specification to specifically recite any subject matter or portion thereof incorporated by reference herein.

In the present specification, unless otherwise indicated, all numerical parameters which have the inherent variability characteristic of the underlying measurement technique used to determine the numerical value of the parameter are to be understood as being referred to and modified in all instances by the term "about". At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter recited in the specification should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Moreover, any numerical range recited in this specification is intended to include all sub-ranges subsumed within that range with the same numerical precision. For example, a range of "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, i.e., all sub-ranges having a minimum value equal to or greater than 1.0 and a maximum value of equal to or less than 10.0, e.g., 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, applicants reserve the right to modify the specification, including the claims, to expressly recite any sub-ranges subsumed within the ranges expressly recited herein. All of these ranges are intended to be inherently described in this specification so that modifications to explicitly recite any such subranges comply with the requirements of 35u.s.c. § 112 and 35u.s.c. § 132 (a).

The grammatical articles "a", "an" and "the" as used in this specification are intended to include "at least one" or "one or more" unless otherwise indicated. Thus, the articles are used in this specification to refer to one or to more than one (i.e., "at least one") of the grammatical objects of the articles. For example, "a component" means one or more components, and thus, more than one component may be considered, and may be employed or used in the practice of the described embodiments. Furthermore, unless the context requires otherwise, the use of a singular noun includes the plural, and the use of a plural noun includes the singular.

As used herein, the term "functionality" refers to the average number of reactive hydroxyl groups (-OH) present per molecule of the-OH functional material. In the preparation of polyurethanes, hydroxyl groups are reacted with isocyanate groups (-NCO), which are attached to isocyanate compounds. The term "hydroxyl number" refers to the number of reactive hydroxyl groups available for reaction and is expressed as milligrams of potassium hydroxide equivalent to the hydroxyl content of one gram of polyol (ASTM D4274-16). The term "equivalent weight" refers to the weight of a compound divided by its valence. For polyols, the equivalent weight is the weight of the polyol to which the isocyanate groups will be bonded, and can be calculated by dividing the molecular weight of the polyol by its functionality. The equivalent weight of the polyol can also be calculated by dividing 56,100 by the hydroxyl number of the polyol — equivalent weight (g/eq) — (56.1x1000)/OH number.

Unless otherwise indicated, the equivalent weights and molecular weights in daltons (Da) given herein are number average equivalent weights and number average molecular weights, respectively, determined by Gel Permeation Chromatography (GPC) using a method based on DIN 55672-1 using chloroform as the eluent and a mixed bed column (Agilent PL Gel; SDVB; 3 micron pore size: 1xMixed-E +5 micron pore size: 2xMixed-D), Refractive Index (RI) measured and calibrated with polyethylene glycol as a standard.

As shown, certain embodiments of the present description relate to laminated components. These laminate parts comprise a core. The core may be metal, plastic, natural material, and/or paper. Suitable metals include aluminum, magnesium, and alloys thereof. Suitable plastics include polyamides, polyesters, polycarbonates, polypropylenes, polystyrenes, ABS, Polyamideimides (PAI), and mixtures thereof. The plastic may be reinforced or non-reinforced, filled or unfilled. Examples of natural materials are wood, flax, sisal, jute and hemp. As used herein, the term "paper" refers to any type of paper, including multi-ply paper, paperboard, and resin-impregnated paper.

In certain embodiments, the core has a plurality of cavities. The cavity may be of any geometric shape. For example, they may be angular or circular channels, holes or bubbles. The cavities may be arranged regularly or irregularly. In some embodiments, the core has a corrugated, angular, honeycomb, or foam-like profile (profile). The core may be, for example, corrugated metal or corrugated cardboard. The core may also be angular rather than corrugated, for example having a rectangular or triangular shape, similar to corrugated metal or corrugated cardboard. Furthermore, the core may also be made of plastic, similar to corrugated metal or corrugated cardboard. For example, angular or corrugated plastic profiles may be extruded. For example, a multi-wall sheet may also be used as the plastic core.

In some embodiments, the core has a thickness of 5 to 50 millimeters. Due to the number of the cavitiesMuch, the weight of the core is generally low relative to its thickness. In some embodiments, the core has a density of 10 to 1000kg/m³。

The laminate component of the present description comprises a fibrous layer arranged on each side of the core. Suitable fibrous layers include, but are not limited to, glass fiber mats, chopped glass strand mats, random glass fiber layers, glass fiber fabrics, cut or milled glass or mineral fibers, natural fiber mats and knit fabrics, cut natural fibers and fiber mats, polymer-based nonwovens and knit fabrics, carbon fibers or aramid fibers, and mixtures thereof. Suitable natural materials for the fibrous layer include, but are not limited to, flax, sisal, jute, and hemp. The fibrous layers on each side of the core may be the same or different.

These fibre layers are arranged on or applied to both sides of the core and are impregnated with polyurethane resin. In some embodiments, the thickness of the fibrous layer is from 0.1 to 2 millimeters. In some embodiments, the weight per unit area of the fibrous layer is from 225 to 1200g/m²。

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 cavity of the core. The urethane resin is used to bond the layers together, and the layers are press-molded under heat before the urethane resin is cured. The polyurethane resin fixes the fibers and forms the surface of the composite part, thereby imparting high strength and rigidity to the layers by bonding them together. This composite material comprising a core and a fibre layer impregnated with polyurethane resin arranged on each side of the core is also referred to herein as a "sandwich structure".

The polyurethane resin system may be a one-component or a multi-component system, such as a two-component system. It may be foamed or non-foamed.

In some embodiments, the polyurethane resin comprises the reaction product of a reaction mixture comprising: (1) at least one polyisocyanate; (2) at least one polyol component having an average OH number of from 300 to 700, in some embodiments the polyol component comprises at least one short chain polyol and one long chain polyol, the initial polyol having a functionality of from 2 to 6; (3) water; (4) an activator; (5) a stabilizer; and optionally, (6) other auxiliary materials, release agents and additives.

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.

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

In certain embodiments, water is used in an amount of 0.1 to 3.0 parts, e.g., 0.3 to 2.0 parts, per 100 parts of the polyol formulation.

Conventional activators for the swelling and crosslinking reaction (e.g., amines or metal salts) may be used for catalysis.

Suitable foam stabilizers include polyether siloxanes, including water-soluble polyether siloxanes. These compounds typically have a copolymer of ethylene oxide and propylene oxide combined with a polydimethylsiloxane group. Foam stabilizers of this type are described, for example, in U.S. Pat. Nos. 2,834,748, 2,917,480, and 3,629,308, the disclosures of which are incorporated herein by reference. Also suitable are polysiloxane-polyoxyalkylene copolymers branched through allophanate (allophanate) groups, as described in U.S. patent nos. 4,096,162 and 4,163,830, the disclosures of which are incorporated herein by reference.

Also suitable are other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, esters of castor oil or ricinoleic acid, turkey red oil and peanut oil, and cell regulators such as paraffin, fatty alcohols and dimethylpolysiloxanes. Oligomeric polyacrylates having polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving and/or stabilizing the emulsifying action, the dispersion of the filler and the porous structure. The surfactant is generally used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the polyol.

Other auxiliary materials, mold release agents and additives may optionally be added to the reaction mixture used to prepare the polyurethane resin. These include, for example, surface-active additives (e.g., emulsifiers), flame retardants, chain extenders, crosslinking agents, nucleating agents, antioxidants, lubricants and mold release agents, dyes, dispersion aids and pigments.

In some embodiments, the ingredients are reacted in amounts such that the equivalent ratio of NCO groups in polyisocyanate component (1) to the sum of ingredients (2) and (3) and hydrogen in (5) which may be reacted with isocyanate groups is from 0.8: 1 to 1.4: 1, for example from 0.9: 1 to 1.3: 1.

In some embodiments, the weight per unit area of the cured polyurethane is from 400 to 1200g/m²。

The aforementioned sandwich structure may be prepared, for example, by applying a fibrous layer on each side of the core and applying an initial polyurethane composition onto the fibrous layer. Alternatively, the fibers may be introduced onto the core by flow of polyurethane feedstock using a suitable mixing head technique. The polyurethane resin can be prepared by, for example, a one-shot process or a prepolymer process.

As previously indicated, the laminate component of the present description further includes an outer layer at least partially coating at least one of the polyurethane impregnated fibrous layers. The outer layer is the cured reaction product of a reaction mixture comprising an organic diisocyanate and/or polyisocyanate (sometimes collectively referred to herein as "isocyanate").

Suitable isocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates. Exemplary isocyanates are those of the formula:

Q(NCO)_n

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

In some embodiments, the isocyanate comprises 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, hexamethylene diisocyanate, and mixtures thereof, Perhydro-2, 4 ' -and 4, 4 ' -diphenylmethane diisocyanate, 1, 3-and 1, 4-phenylene diisocyanate, 1, 4-Durene Diisocyanate (DDI), 4 ' -stilbene diisocyanate (stilbene), 3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate (TODI), 2, 4-and 2, 6-Toluene Diisocyanate (TDI) and any mixtures of these isomers, diphenylmethane-2, 4 ' -and/or 4, 4 ' -diphenylmethane diisocyanate (MDI), naphthylene-1, 5-diisocyanate (NDI), or a mixture of any two or more thereof.

Other suitable isocyanates include triphenylmethane-4, 4', 4 "-triisocyanate, polyphenyl-polymethylene polyisocyanates (as obtained by condensation of aniline with formaldehyde and subsequent phosgenation), m-and p-isocyanatophenylsulfonyl isocyanates, perchloroaryl polyisocyanates, polyisocyanates having carbodiimide groups, norbornane (norbonane) diisocyanates, polyisocyanates having allophanate groups, polyisocyanates having isocyanurate groups, polyisocyanates having urethane (urethane) groups, polyisocyanates having acylated urea groups, polyisocyanates having biuret groups, polyisocyanates prepared by telomerization (telomerization) reaction, polyisocyanates having ester groups, polyisocyanates having isocyanate groups, polyisocyanates, and mixtures of the polyisocyanates, and the polyisocyanates, and the polyisocyanates, and the polyisocyanates, and, Reaction products of the above isocyanates with acetals, and polyisocyanates containing polymeric fatty acid esters.

Mixtures of any two or more of the above polyisocyanates can of course be used.

However, in some embodiments, the isocyanates include 2, 4-and 2, 6-toluene diisocyanate and any mixture of these isomers ("TDI"), 4 '-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate and polyphenyl-polymethylene polyisocyanate ("crude MDI"), which is prepared by condensation of aniline with formaldehyde and subsequent phosgenation, and polyisocyanates having carbodiimide groups, uretonimine groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups ("modified polyisocyanates"), in particular those derived from 2, 4-toluene diisocyanate and/or 2, 6-tolylene diisocyanate or these modified polyisocyanates derived from 4, 4 '-diphenylmethane diisocyanate and/or 2, 4' -diphenylmethane diisocyanate. Also suitable are naphthylene-1, 5-diisocyanates and mixtures of the abovementioned polyisocyanates.

In some embodiments, the isocyanate comprises a prepolymer having isocyanate groups prepared by: the polyol and/or chain extender and/or crosslinker are reacted with at least one aromatic diisocyanate selected from the group consisting of TDI, MDI, TODI, DIBDI, NDI and DDI, for example 4, 4' -MDI, to give a polyaddition product having urethane groups and isocyanate groups and an NCO content of 6 to 25% by weight.

In certain embodiments, the polyisocyanate comprises a methylene bridged polyphenyl polyisocyanate and/or a prepolymer of a methylene bridged polyphenyl polyisocyanate having an average functionality of from 1.8 to 3.5, such as from 2.0 to 3.1, isocyanate moieties per molecule and an NCO content of from 20 to 32 weight percent.

The reaction mixture used to form the outer layer that at least partially coats at least one of the polyurethane impregnated fibrous layers also comprises a polyether polyol having a molecular weight of 800Da to 25,000Da, such as 800 to 14,000Da, or in some cases, 1,000 to 8,000Da, and a functionality of 2 to 8, such as 2.4 to 8, or 2.5 to 3.5.

Specific examples of suitable polyether polyols having molecular weights and functionalities within the above ranges include polyoxyethylene glycols, triols, tetrols and higher functionality polyoxyethylene polyols, polyoxypropylene glycols, triols, tetrols and higher functionality polyoxyethylene polyols, and mixtures thereof. When mixtures are used, the ethylene oxide and propylene oxide may be added simultaneously or sequentially to provide internal blocks, terminal blocks or random distribution of the oxyethylene groups and/or oxypropylene groups in the polyether polyol. Suitable initiators or initiators for these compounds include, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, ethylenediamine, and toluenediamine, and mixtures of any two or more thereof. The alkoxylation reaction can be catalyzed using any conventional catalyst including, for example, potassium hydroxide (KOH) or Double Metal Cyanide (DMC) catalysts.

Other suitable polyether polyols include alkylene oxide adducts of non-reducing sugars and sugar derivatives, alkylene oxide adducts of phosphoric and polyphosphoric acids, alkylene oxide adducts of polyphenols, polyols prepared from natural oils (e.g., castor oil), and alkylene oxide adducts of polyhydroxyalkanes other than those described above.

Exemplary alkylene oxide adducts of polyhydroxyalkanes include, for example, alkylene oxide adducts of polyhydroxyalkanes such as: 1, 3-dihydroxypropane, 1, 3-dihydroxybutane, 1, 4-dihydroxyhexane, 1, 5-and 1, 6-dihydroxyhexane, 1, 2-dihydroxyoctane, 1, 3-dihydroxyoctane, 1, 4-dihydroxyoctane, 1, 6-and 1, 8-dihydroxyoctane, 1, 10-dihydroxydecane, glycerol, 1, 2, 4-trihydroxybutane, 1, 2, 6-trihydroxyhexane, 1, 1, 1-trimethylolethane, 1, 1, 1-trimethylolpropane, pentaerythritol, caprolactone, polycaprolactone, xylitol, arabitol, sorbitol, mannitol, and the like.

Other polyols which may be used include alkylene oxide adducts of non-reducing sugars wherein the alkoxide has from 2 to 4 carbon atoms. Non-reducing sugars and sugar derivatives include sucrose, alkyl glycosides (e.g., methyl glycoside and ethyl glycoside), glycol glycosides (e.g., ethylene glycol glycoside, propylene glycol glycoside), glycerol glycoside and 1, 2, 6-hexanetriol glycoside, and alkylene oxide adducts of alkyl glycosides.

Other suitable polyether polyols include polyphenols such as alkylene oxide adducts thereof, wherein the alkylene oxides have from 2 to 4 carbon atoms. Suitable polyphenols are, for example, bisphenol a, bisphenol F, condensation products of phenol and formaldehyde, novolac resins (novolac resin), condensation products of various phenolic compounds and acrolein (including 1, 1, 3-tris (hydroxy-phenyl) propane), condensation products of various phenolic compounds and glyoxal, glutaraldehyde, other dialdehydes (including 1, 1, 2, 2-tetrakis (hydroxyphenol) ethane).

Alkylene oxide adducts of phosphoric and polyphosphoric acids are also suitable. These include ethylene oxide, 1, 2-propylene oxide, butylene oxide, 3-chloro-1, 2-propylene oxide as alkylene oxides. Phosphoric acid (phosphoric acid), phosphorous acid (phosphoric acid), polyphosphoric acids (e.g., tripolyphosphoric acid (tripolyphosphoric acid)), and polymetaphosphoric acids (polymetaphosphoric acids) are suitable.

In certain embodiments, the polyether polyol has a molecular weight of from 800Da to 25,000Da, such as from 800 to 14,000Da, or, in some cases, from 1,000 to 8,000Da, and a functionality of from 2 to 8, such as from 2.4 to 8, or from 2.5 to 3.5, present in an amount of at least 50 weight percent, such as at least 80 weight percent, based on the total weight of isocyanate-reactive ingredients in the reaction mixture.

In addition, a low molecular difunctional chain extender, a trifunctional or tetrafunctional crosslinker or a mixture of chain extender and crosslinker may be present in the reaction mixture for forming the outer layer. Suitable chain extenders (e.g., alkanediols, dialkylene glycols, and polyalkylene polyols) and crosslinkers (e.g., 3-or 4-valent alcohols having a functionality of 3 to 4 and oligomeric polyalkylene polyols) typically have a molecular weight of < 750g/mol, for example 18 to 400g/mol or 60 to 300 g/mol. Alkanediols having 2 to 12 (e.g. 2, 4 or 6) carbon atoms (including ethylene glycol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 4-butanediol) and dialkylene glycols having 4 to 8 carbon atoms (e.g. diethylene glycol and dipropylene glycol) and polyoxyalkylene glycols are suitable chain extenders. Also suitable are branched and/or unsaturated alkanediols having generally not more than 12 carbon atoms, such as 1, 2-propanediol, 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2-butene-1, 4-diol and 2-butyne-1, 4-diol; diesters of terephthalic acid with diols having 2 to 4 carbon atoms, such as terephthalic acid-bis-ethylene glycol or terephthalic acid-bis-1, 4-butanediol; hydroxyalkylene ethers of hydroquinone or resorcinol, such as 1, 4-bis- (. beta. -hydroxyethyl) -hydroquinone or 1, 3- (. beta. -hydroxyethyl) -resorcinol; alkanolamines having 2 to 12 carbon atoms, such as ethanolamine, 2-aminopropanol and 3-amino-2, 2-dimethylpropanol; n-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine; (cyclo) aliphatic diamines having 2 to 15 carbon atoms, such as 1, 2-ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine and 1, 6-hexamethylenediamine, isophoronediamine, 1, 4-cyclohexanediamine and 4, 4' -diaminodicyclohexylmethane; n-alkyl-, N ' -dialkyl-substituted aromatic diamines, which may also be substituted on the aromatic radical by alkyl groups and have 1 to 20, for example 1 to 4, carbon atoms in the N-alkyl group, such as N, N ' -diethyl-, N ' -di-sec-pentyl-, N ' -di-sec-hexyl-, N ' -di-sec-decyl-and N, N ' -dicyclohexyl-, (p-or m) -phenylenediamine, N ' -dimethyl-, N ' -diethyl-, N ' -diisopropyl-, N ' -di-sec-butyl-, N ' -dicyclohexyl-, 4 ' -diamino-diphenylmethane, N ' -di-butyl-, N ' -dicyclohexyl-, N ' -di-sec-butyl-, N ' -dicyclohexyl-, 4 ' -diamino-diphenylmethane, N ' -di-butyl-, N ' -di-sec-pentyl-, N ' -hexyl-, N ' -di-sec-hexyl-, N ' -di-hexyl-, N ' -di-sec-hexyl-, N ' -di-hexyl-, N ' -di-hexyl-, di-phenyl-diamine, N, n, N '-di-sec-butylbenzidine, methylene-bis (4-amino-3-benzoic acid methyl ester), 2, 4-chloro-4, 4' -diamino-diphenylmethane, 2, 4-toluenediamine and 2, 6-toluenediamine.

In certain embodiments, the chain extender and/or cross-linker is present in an amount of no greater than 50 weight percent, such as no greater than 20 weight percent, for example from 1 to 50 weight percent or from 2 to 20 weight percent, based on the total weight of isocyanate-reactive ingredients in the reaction mixture.

As shown, the reaction mixture used to form the outer layer in the laminate part of the present description comprises 0.5 to 15 wt.%, e.g., 0.5 to 5 wt.% of a fatty acid ester lubricant. As will be appreciated, a "fatty acid ester" is a product resulting from esterification of an alcohol with a fatty acid.

Suitable fatty acid esters include, but are not limited to, ester reaction products of fatty acids having from 5 to 32 carbon atoms, such as from 12 to 22 carbon atoms, with monohydric or polyhydric alcohols having from 2 to 30 carbon atoms, such as from 2 to 22 carbon atoms.

Specific examples of suitable fatty acids include saturated fatty acids such as caproic acid, caprylic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid (myristic acid), stearic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid, and unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, brassidic acid, erucic acid, and ricinoleic acid, and mixtures of any two or more thereof. Specific examples of suitable alcohols for forming the esters include monohydric alcohols such as propanol, isopropanol, butanol, octanol (capryl alcohol), octanol (captyl alcohol), lauryl alcohol, myristyl alcohol, stearyl alcohol, and behenyl alcohol, and polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, glycerol, trimethylolpropane, pentaerythritol, isotridecanol, and neopentyl glycol, and mixtures of any two or more thereof.

The fatty acid ester lubricant used in the reaction mixture for forming the outer layer has an isocyanate-reactive (e.g., hydroxyl) functionality of at least 1, such as 1 to 2. In certain embodiments, the fatty acid ester lubricant has a hydroxyl number of at least 10mg KOH/g, such as 10 to 50mg KOH/g or 10 to 20mg KOH/g.

It has been found that the inclusion of the fatty acid ester lubricant in the above amounts allows for the effective use of a non-reactive, silicon-free, non-transfer, non-marking external mold release agent on the mold cavity surface, as described below, but surprisingly does not result in a surface of the resulting outer layer lacking the slip resistance required for the use of the resulting laminate as a load-bearing floor in, for example, an automobile. This is unexpected because fatty acid esters are known to act as lubricants to impart anti-friction sliding or gliding properties to polymers. Furthermore, it has been found that an outer layer having weather resistant (weather able) and class a surfaces can be prepared without "streaking" from the transfer of external mold release agents from the mold cavity surface to the outer layer of the laminate.

The reaction mixture used to form the outer layer may also contain other ingredients, such as catalysts and other additives.

Suitable catalysts include amine catalysts, such as tertiary amines. Exemplary tertiary amines include triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N' -tetramethylethylenediamine, pentamethyldiethylenetriamine and higher nuclear 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-phenyl-ethylamine, bis- (dimethylaminopropyl) urea, N-ethylmorpholine, N, N, N ', N' -dimethyldiethylenetriamine and higher nuclear homologues, N, N ', N' -dimethylethylenediamine, N, N-dimethylaminoalkyl-dimethyl-B-phenylethylamine, N, N-diethylbenzylamine, bis- (dimethylaminopropyl) urea, N-dimethylaminoethyl-piperazine, N, N-methyl-N, N, N, N '-dimethylaminoethyl-piperazine, N, N, N' -dimethylol, N, N, Bis- (dimethylaminopropyl) amine, 1, 2-dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic amidines, bis- (dialkylamino) -alkyl ethers (e.g., bis (dimethylaminoethyl) ether), and tertiary amines having an amide group (e.g., a carboxamide group). Mannich bases (Mannich bases) composed of secondary amines (e.g. dimethylamine) and aldehydes (e.g. formaldehyde) or ketones (e.g. acetone, methyl ethyl ketone or cyclohexanone) and phenols (e.g. phenol, nonylphenol or bisphenol) are also suitable as catalysts. Tertiary amines having active hydrogen atoms in relation to isocyanate groups as catalysts are, for example, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-dimethylethanolamine, their reaction products with alkylene oxides, such as propylene oxide and/or ethylene oxide, and secondary tertiary amines. Amines having carbon-silicon bonds, such as 2, 2, 4-trimethyl-2-silamorpholine (silamorphine) and 1, 3-diethylaminomethyl tetramethyldisiloxane, can be used as catalysts. In addition, nitrogen-containing bases such as tetraalkylammonium hydroxides, and hexahydrotriazines are also suitable catalysts.

In addition to or in place of the amine catalyst described above, a metal catalyst may be used. Specific examples of such catalysts include organometallic compounds of tin, titanium, bismuth, and in particular organotin compounds. Tin (II) salts of carboxylic acids, such as tin (II) acetate, tin (II) octoate, 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, can be used.

Various other additives may be included in the reaction mixture forming the outer layer. These include, but are not limited to, emulsifiers, foam stabilizers, cell regulators, flame retardants, uv stabilizers, nucleating agents, oxidation retarders, stabilizers, colorants, dispersants, and pigments.

Certain embodiments of the present description relate to methods of making laminated parts. 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.

To improve demolding, the inner wall of the mold used is optionally coated with an external mold release agent. Indeed, one feature of the process of the present specification is the use of a non-reactive, silicon-free external mold release agent, such as a non-transfer wax. In fact, it was found that using a specific combination of reaction mixtures comprising fatty acid esters having an isocyanate reactive functionality of at least 1 (e.g. a functionality of 1 to 2) as described above, together with a non-reactive silicon-free external mould release agent (e.g. a non-transfer wax), it was possible to prepare up to 15 laminate parts having an outer layer with a water-repellent, non-slip and class a surface quality top coat, all without the need for further application of an external mould release agent.

As will be appreciated, many mold release agents use silicones as a base component due to their inherent lubricating properties. However, silicone-based mold release agents have several disadvantages. First, it is not possible to paint or glue the component directly after molding, since the silicone residues remaining on the component do not allow the paint or adhesive to form a bond with the component. The assembly needs to be thoroughly cleaned before bonding with the paint or glue, which is undesirable for time and cost reasons. Secondly, silicone-based release agents can cause the surface of the part to feel greasy. Third, many silicone-based release agents react with the polyurethane-forming components used in the outer layer described herein such that they adhere better to the polyurethane layer than to the tool (tool), resulting in their removal from the tool (while remaining bonded to the outer layer) when the laminated part is removed from the tool.

According to the method of the present description, a sandwich structure of the type described earlier is inserted into the mould cavity and the mould is closed. The outer layer at least partially coating at least one of the polyurethane impregnated fibrous layers of the sandwich structure is then prepared by using a reaction injection moulding technique (RIM process). In certain embodiments, the amounts of the components of the reaction mixture forming the 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. As will be understood, "isocyanate index" means the quotient of the number of isocyanate groups and the number of isocyanate-reactive groups multiplied by 100.

In some embodiments, the initial temperature of the reaction mixture introduced into the mold is from 20 ℃ to 80 ℃, e.g., from 30 ℃ to 70 ℃, and in some embodiments, the temperature of the mold is from 30 ℃ to 130 ℃, e.g., from 40 ℃ to 80 ℃.

The method of the present description includes reacting the reaction mixture in the mold to form an outer layer at least partially coating at least one of the polyurethane-impregnated fiber layers, and then removing the laminate part from the mold. In some embodiments, the molded laminate part is removed from the mold, i.e., demolded after a mold residence time of 5 to 180 seconds. In some cases, conditioning may be carried out at a temperature of about 60 ℃ to 180 ℃ for 30 to 120 minutes after demolding.

As shown, the outer layer described herein at least partially coats at least one of the polyurethane impregnated fiber layers. In some embodiments, the outer layer at least partially coats two of the polyurethane fiber layers. In some embodiments, the outer layer described herein completely or substantially completely coats one or both of the polyurethane-impregnated fibrous layers. Where the outer layer described herein does not at least partially coat one of the polyurethane impregnated fibrous layers, that layer may have another layer, such as a decorative layer deposited thereon, as desired. The layer may comprise, for example, a metal foil or sheet, a dense thermoplastic composite made of, for example, PMMA (polymethylmethacrylate), ASA (acrylate-modified styrene acrylonitrile terpolymer), PC (polycarbonate), PA (polyamide), PBT (polybutylene terephthalate), and/or PPO (polyphenylene oxide). Alternatively, the layer may be constructed of a fabric material with a barrier of TPU (thermoplastic polyurethane) sheets, dense or foam sheets, and other spray or RIM polyurethane skin layers.

Some suitable applications for the laminate parts of the present description in the automotive industry include, for example, roofs, hoods, tailplanes, door or floor modules, and load-bearing floors.

The following non-limiting and non-exhaustive examples are intended to further describe various non-limiting and non-exhaustive embodiments, but not to limit the scope of the various embodiments described in this specification.

Examples

Examples

The die used for the experiments described below was a 12 inch by 8 inch by 0.125 inch plate die. The die was mounted on a press adjacent to a small cylindrical RIM machine. The mold had a "peanut" style edge-gated injection site after the mixer. The mold was heated to 175 ° F with a waterline. The heat is maintained by circulating water at the desired temperature with the electric heater unit.

For each experiment, the tool was thoroughly cleaned using Chem Trend mold cleaner MOC-10003 (N-methyl pyrrolidone) to remove any residual external mold release agent, and then wiped with water to neutralize any remaining mold cleaner. The tool was made by spraying an external release agent coating (listed in table 1), wiping with a soft cloth, and spraying the external release agent again.

For each experiment, the RIM machine throughput was set at 500 grams/second, and the batch temperature was maintained at 110 ℃ F. for the "B" POLYOL SIDE ("B" POLYOL SIDE) and at 100 ℃ F. for the "A" isocyanate SIDE ("A" ISO SIDE). The injection weight was set to 230 grams in total and the material was injected into the mold. The tool was kept closed for 40 seconds before separating the halves and opening the tool and the demolded part.

For each experiment, the "B" polyol side was prepared using the same amounts of the following ingredients: 1) a polyol blend which is a mixture of: i)83.2 parts of a glycerol-based triol polyol having a molecular weight of 4700, ii)3.74 parts of ethylene glycol, and iii)2.06 parts of an ethylenediamine-initiated tetrafunctional polyol having a molecular weight of 356; triethylenediamine catalyst from Evonik to33LV was sold; 3) tin carboxylate catalyst from MomentiveSold under UL-38; 4) CAT C, a blocking type DBU catalyst sold by Momentive as Niax A-575; delayed action tertiary amine catalysts, available from Evonik to1028 obtaining; 6) pigment dispersions of carbon black and black dye, supplied by Chromaflo as Colormatch DR-2205; and 7) an antioxidant package provided as Tinuvin B-75 by Chromaflo in liquid form. In addition, the "B" polyol side contains the additives in the amounts listed in table 1 (weight%, based on the total weight of the "B" polyol side). In each case, the "A" isocyanate side is a liquid modified 4, 4-diphenylmethane-diisocyanate (MDI) prepolymer having an average NCO group number of 22.6 to 23.1 and a viscosity of 550-800cps at 25 ℃, and the "B" polyol side is blended with the "A" isocyanate side at a ratio of 100: 47 ("B" polyol side: "A" isocyanate side) were mixed in a weight ratio.

Additive A:g71, a hydroxyl functionality of 1.5 and an OH number of 12.5mg KOH-g of a fatty acid ester lubricant, commercially available from Albemarle.

And (3) an additive B:INT-1324, a fatty acid ester lubricant believed to be free of isocyanate-reactive functionality, is commercially available from Axel Plastics Research Laboratories, Inc.

EMR-1：XTEND^TMW-7806R, an aqueous emulsion of a resin and a surfactant, which crosslinks to form a semi-permanent release film (release film), is commercially available from Axel Plastics Research Laboratories, Inc.

EMR-2：XTEND^TMW-4016, an aqueous emulsion of a resin, a crosslinker, and a surfactant, which crosslinks to form a semi-permanent release film, is commercially available from Axel Plastics Research Laboratories, Inc.

EMR-3：XTEND^TM19RSS, an air-dried reactive resin solution that cures to a crosslinked semi-permanent coating, organic solvent based, commercially available from Axel Plastics Research Laboratories, inc.

EMR-4: chem Trend PU-12004: naptha-based wax emulsions, available from Chem-Trend l.p.

TABLE 1

Each example can evaluate the number of releases achieved with a single application of EMR and the surface quality of the laminate part. The results are shown in Table 2.

Examples	# demolded	Surface quality
			1	10+	Smooth/mottle
2	11	Surface-dried, drawn parts
			3	12	Additive exudation from the part after 24 hours
4	18	Additive exudation from the part after 24 hours
			5	10	Additive exudation from the part after 24 hours
6	11＊	Good surface quality and easy demoulding
			7	10	After 5 times of demoulding, the surface has spots

The parts are easily demolded and have a defect-free or over-demolded surface. The surface has a "gripyy" feel. The part was then trimmed to a final weight of 205 to 210 grams to form a molded density of about 65 pounds per cubic foot. The injection was repeated without further application of an external mold release agent. It was determined that the parts adhered and deformed after about 15 injections. The release agent was then reapplied by using only one spray application and the experiment was repeated for a further 15 injections before the parts were stuck. It is believed that multiple releases with good part surface quality have been achieved at this time. In the case of a polyol mixture without additive a and using the same external mold release agent, only one part can be successfully demolded. The second injection with this type of polyol causes part sticking and distortion.

Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.