polyamide-metal laminate

Abstract

A novel polyamide-metal laminate having desirable hydrolytic resistance is provided. The laminate comprises (A) a metal, (B) a tie layer, and (C) a polyamide composition. The tie layer is composed of (B1) a polymer containing a comonomer having at least two adjacent carboxylic acid groups and (B2) a composition containing an amino-silane containing a primary amine and at least one hydroxyl group.

Description

Technology Field

[0001] Cross-reference regarding related applications

[0002] The present application claims priority under 35 USC § 365 to U.S. Provisional Application No. 62 / 940,397 filed November 26, 2019, the entire contents of which are incorporated herein by reference.

[0003] Technology field

[0004] To more fully explain the level of art to which the present invention belongs, several patents and published documents are incorporated herein by reference. The full disclosure of each of these patents and published documents is incorporated herein by reference.

[0005] A novel polyamide-metal laminate is disclosed herein, comprising a novel tie layer for bonding a polyamide composition to a metal surface, having desirable hydrolytic resistance. Additionally, a composition suitable for forming a tie layer on a metal, a metal part having a tie layer, an article comprising said polyamide-metal laminate, and a process for manufacturing said polyamide-metal laminate are disclosed herein. Background Technology

[0006] Polyamide-based compositions typically possess desirable chemical resistance, processability, and heat resistance. These characteristics make them highly suitable for requirements in high-performance automotive and electrical / electronic applications, such as vehicle radiators and heater hoses. Currently, there is a general demand in the automotive sector to continuously reduce the weight of the various components that make up a vehicle.

[0007] U.S. Patent Application Publication No. 2003 / 0116269 discloses an aqueous primer composition comprising an organosilane for use on a metal surface primarily to bond two metals together. U.S. Patent Application Publication No. 2003 / 0180552 discloses a method for improving the adhesion of a polymer to a metal surface by treating a metal surface with a silane composition. U.S. Patent Application Publication No. 2007 / 0056469 discloses a method for improving the adhesion of a polymer to a metal surface by treating a metal surface with a silane composition. The silane composition comprises a silane coating composition containing at least one water-soluble or water-dispersible silane and a polymer resin. The polymer resin is water-insoluble and is used as an aqueous dispersion.

[0008] Nevertheless, there is still a need for much lighter articles used to manufacture components applied to the engine compartment of a vehicle, which consist of fewer parts than currently available automotive components and are easier to manufacture. Direct bonding of aluminum or other lightweight metals to polyamide eliminates parts and provides lighter articles. However, such direct bonding must be able to withstand the high temperatures found in the engine compartment of a vehicle, particularly when the article is exposed to a high-temperature aqueous solution of ethylene glycol. Brief explanation of the drawing

[0009] FIG. 1 shows a schematic diagram of the expected chemical structure of the metal (A), tie layer (B), and polyamide (C) for a stacked polyamide-aluminum. Figure 2 illustrates a schematic diagram of the expected chemical structure after the tie layer (B) is formed on aluminum (A). Figure 3 illustrates a schematic diagram of another chemical structure expected after the tie layer (B) is formed on aluminum (A). FIG. 4 illustrates a schematic diagram of the expected chemical structure when amino silane (B2) is not included in the tie layer (B) (comparison). FIG. 5 illustrates a schematic diagram of the expected chemical structure when the carboxylic acid-containing polymer (B1) is not included in the tie layer (B) (comparison). Figure 6 shows a side cross-sectional view of a polyamide cap test sample. FIG. 7 shows a side cross-sectional view of a polyamide cap test sample in a lamination device for laminating onto a metal layer through a tie layer to form a polyamide-metal laminate having a tie layer. Figure 8 shows a side cross-sectional view of a polyamide-metal laminate having a tie layer in a device for determining the adhesion strength between a polyamide cap test sample and a metal layer. Figure 9 shows a perspective view of a test sample for determining adhesive strength according to ISO-19095-3. Specific details for implementing the invention

[0010] abbreviation

[0011] The claims and descriptions herein shall be interpreted using the abbreviations and definitions set forth below.

[0012] "h" and "hr" refer to time.

[0013] "%" refers to the term "percent".

[0014] "Mol%" refers to mole percentage.

[0015] "Weight %" refers to weight percentage.

[0016] "Bu" refers to the weight portion.

[0017] "g" refers to a gram.

[0018] definition

[0019] The singular form used herein refers not only to one but to more than one, and does not necessarily limit its referents to the grammatical category of the singular.

[0020] As used herein, the term "Article" refers to an item, object, structure, object, component, device, etc., that is in a form, shape, or configuration suitable for a specific use or purpose without further processing of the whole or any part thereof. An Article may include one or more component(s) or subassembly(s) that are partially completed and awaiting further processing, or that, when combined with other components or subassemblies, form a finished product. Additionally, as used herein, the term "Article" may refer to a system or configuration of an Article.

[0021] As used herein, the term "solution" refers to an aqueous mixture of components that can be dissolved, suspended, or dispersed in water, alcohol, other suitable liquids, or a combination of two or more suitable liquids.

[0022] The term "pure aluminum" as used herein refers to an aluminum metal containing at least 99 weight percent of aluminum based on the total weight of the pure aluminum.

[0023] The term "aluminum alloy" as used herein refers to an aluminum metal comprising less than 99 weight percent aluminum based on the total weight of the alloy, and comprising one or more other metals and optionally one or more non-metallic elements.

[0024] As used herein, the term "tie layer" refers to a composition in which a metal is bonded to a polyamide composition without the need for mechanical bonding, although additional bonding by mechanical means is optional if desired. The tie layer forms a sandwich structure in which the tie layer is an intermediate layer, one outer layer or outer layer in which the metal is directly bonded to the tie layer, and another outer layer in which the polyamide composition is directly bonded to the tie layer. In other words, the metal layer is directly bonded to one side of the tie layer, and the polyamide composition is directly bonded to the opposite side of the tie layer.

[0025] Range and preferred variations

[0026] All ranges set forth herein clearly include their endpoints unless otherwise expressly stated. Denoting a quantity, concentration, or other value or parameter as a range specifically discloses all possible ranges formed from any possible upper range and any possible lower range, regardless of whether such pairs of upper and lower ranges are expressly disclosed herein. The compounds, processes, and articles described herein are not limited to the specific values ​​disclosed in defining ranges in this specification.

[0027] Any variations of materials, chemicals, methods, steps, values, and / or ranges, etc., disclosed herein regarding the processes, compounds, and articles described herein are intended to include all possible combinations of such variations having any other materials, methods, steps, values, ranges, etc., specifically described herein, regardless of whether they are identified as preferred. Any combination of disclosed features is a preferred variation of the processes, compounds, and articles described herein.

[0028] General Overview

[0029] A polyamide-metal laminate comprising a polyamide composition bonded to a metal using a tie layer of a specific composition is described herein. Preferably, the polyamide-metal laminate exhibits desirable hydrolytic resistance when exposed to ethylene glycol / aqueous solution for 1,000 hours at 130°C compared to the initial bonding strength before exposure to ethylene glycol / aqueous solution.

[0030] In addition, a tie layer used to improve the bonding of metals to a polyamide composition and a process for manufacturing such a tie layer are described herein.

[0031] Also preferably, the polyamide-metal laminate comprises (A) a metal, (B) a tie layer formed on the surface of the metal, and (C) a polyamide formed on the surface of the tie layer, wherein the tie layer

[0032] B1) A polymer containing a carboxylic acid group; and

[0033] B2) Amino-silane comprising a primary amine and at least one hydroxyl group

[0034] Includes,

[0035] At least two carboxylic acid groups in the polymer (B1) are adjacent to each other, and the molar ratio of two adjacent carboxylic acid groups in (B1) to primary amine groups in (B2) is 1:0.8 to 1:14.

[0036] Additionally, a composition comprising the above-described (B1) and (B2), a metal part having a tie layer (B), a process for manufacturing a polyamide metal laminate, and an article comprising the polyamide metal laminate are described herein.

[0037] polyamide-metal laminate

[0038] The polyamide-metal laminate disclosed herein may be used to manufacture a polyamide hose (polyamide (C)) bonded to a metal radiator (metal (A)) using an article having any shape, such as a tie layer (B). The tie layer (B) disclosed herein may be applied or coated onto the metal (A) to provide a tie / metal laminate. Such a tie / metal laminate may subsequently be bonded to a polyamide composition to manufacture a polyamide-metal laminate.

[0039] metal layer (A)

[0040] The metal (A) may be any metal capable of forming a bond with the hydroxyl group of the aminosilane (B2). Examples of the metal (A) include carbon steel, galvanized steel, stainless steel, steel casting, aluminum, titanium, and alloys thereof. The metal (A) is preferably a light metal, such as aluminum or titanium, preferably aluminum. The metal may be a pure metal or a metal alloy. A metal alloy may comprise a mixture of metals. Alternatively, one or more metals may be combined with one or more non-metallic elements, such as carbon or silicon, to form an alloy. If the metal is aluminum, the aluminum content of the aluminum alloy should be at least about 70 weight percent aluminum, preferably at least about 80 weight percent aluminum, more preferably at least 90 weight percent aluminum.

[0041] metal surface cleaning

[0042] Before forming the tie layer (B) on the metal (A), cleaning of the metal surface may or may not be necessary. If cleaning of the metal surface is necessary, methods typically used in the art to remove contaminants and oxidation from the metal surface may be used. Cleaning of the metal surface includes both chemical treatment and mechanical methods, and combinations of two or more suitable cleaning methods. Examples of such cleaning methods include, without limitation, polishing; grinding with abrasive materials, such as sandpaper; atmospheric pressure plasma treatment, corona discharge treatment; shot blasting; cleaning with cleaning solutions, detergent solutions, solvents, or deionized water; and chemical etching. When polishing the metal, a solution containing abrasive materials may be used. Non-limiting examples of abrasive materials include calcium carbonate, sodium bicarbonate, calcium sulfate, magnesium sulfate, and combinations thereof. The solution may also include alcohols, such as ethyl alcohol, methyl alcohol, and isopropyl alcohol. The cleaning solution preferably contains a cationic, anionic, or nonionic surfactant, or a combination of two or more surfactants. The cleaning solution may be any detergent or surfactant solution capable of removing contaminants on a metal surface. Examples of suitable cleaning solutions are well known in the art.

[0043] If the metal is aluminum or an aluminum alloy, the aluminum must be cleaned so that it can react with the aminosilane (B2). Any cleaning method may be used. A preferred method for cleaning the aluminum or aluminum alloy is polishing the surface of the aluminum or aluminum alloy with an abrasive material such as sandpaper in water or shot blasting. Without being bound by theory, the surface of the aluminum is considered to need to be cleaned and optionally activated to achieve sufficient hydrolytic resistance to form a polyamide-metal laminate. One example for analyzing the surface of the aluminum is X-ray photoelectron spectroscopy (XPS). Typically, the surface of the aluminum or aluminum alloy is oxidized or contaminated by oil, so signals of carbon and oxygen atoms are observed in addition to the aluminum signal. To achieve sufficient hydrolytic resistance to form a polyamide-metal laminate, the aluminum signal analyzed by XPS must be at least 15%, preferably at least 20%. The percentage of the aluminum signal is based on the total moles of elements present on the aluminum surface. Alternatively, the percentage is "atomic %" based on the total number of atoms detected in the analysis, after applying a relative sensitivity factor and appropriately integrating the peak areas of the XPS spectrometry. Another example for analyzing the surface of aluminum is Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). Again, without being bound by theory, hydroxyl group(s) are considered to be present on the surface of aluminum to achieve sufficient hydrolytic resistance for the polyamide-metal laminate. The number of hydroxyl groups is analyzed by TOF-SIMS as an aluminum hydroxide signal (Al(OH)3 or AlO(OH)·nH2O).

[0044] Tie layer (B)

[0045] A tie layer (B) that can be used to manufacture the polyamide-metal laminate described herein comprises a polymer (B1) and an amino-silane (B2). The polymer (B1) comprises a carboxylic acid group. The amino-silane (B2) comprises a primary amine group and at least one hydroxyl group within the amino-silane molecule. The tie layer (B) may be a mixture of the polymer (B1) and the amino-silane (B2), or a reaction product of the polymer (B1) and the amino-silane (B2). If the tie layer (B) is a reaction product, the carboxylic acid group of the polymer (B1) reacts with the amino group of the amino-silane (B2). In some preferred tie layers, this reaction forms a cyclic imide in which the silane group is pendanted from the imide nitrogen. The reaction between the carboxylic acid group of the polymer (B1) and the amino group of the amino-silane (B2) is believed to occur when heated, for example, to a temperature of 220°C or higher.

[0046] Polymer (B1)

[0047] The polymer (B1) used to manufacture the tie layer (B) contains carboxylic acid groups. The carboxylic acid groups may be derivatives of carboxylic acid groups, for example, without limitation, carboxylic acid salts, alkyl esters including monoesters and diesters, or carboxylic acid anhydrides. At least two carboxylic acid groups in (B1) must be adjacent to each other. Preferably, adjacent carboxylic acid groups are derived from copolymer units of an anhydride group, for example, maleic anhydride, because the anhydride group provides two adjacent carboxylic acid groups when hydrolyzed. The adjacent carboxylic acid groups contribute to the formation of a cyclic imide structure having a nitrogen atom of an amino group, as described below.

[0048] Typically, the polymer (B1) can be prepared by copolymerizing one or more monomers (B1-a) having an ethylene unsaturated group and one or more monomers (B1-b) having an ethylene unsaturated group and at least two adjacent carboxylic acid groups or derivatives thereof. As used herein, the term “adjacent carboxylic acid groups” refers to a molecule in which at least two carbon atoms are directly bonded to each other by a single or double bond, and each of these at least two carbon atoms is substituted by a carboxylic acid. The monomer (B1-a) may also have a carboxylic acid group. The monomer (B1-a) having an ethylene unsaturated group may include, without limitation, unsaturated aliphatic hydrocarbons, such as ethylene, propylene, butene, octene, and isopropylene; aromatic monomers, such as styrene and 4-methylstyrene; acrylic acid; methacrylic acid; acrylates, such as acrylic acid salts or esters; methacrylates, such as methacrylate salts or esters; and combinations of two or more of these are included. Preferred monomers (B1-b) having a dicarboxylic acid group or a derivative thereof include, without limitation, maleic acid, fumaric acid, itaconic acid, citraconic acid, and derivatives of these acids, such as acid anhydrides, salts, diesters, and monoesters. Maleic anhydrides and alkyl monoesters of maleic acid are preferred. In the copolymer of monomer (B1-a) and monomer (B1-b), the preferred molar content of the residue of monomer (B1-b) is 10 mol% or more, more preferably 20 mol% or more, and even more preferably 40 mol% or more, based on the total copolymerized moles of (B1-a) and (B1-b). The content of two adjacent carboxylic acid groups in the polymer (B1) may be 2 weight% or more, preferably 5 weight% or more, based on the total weight% of the polymer (B1). The remaining copolymerized unit of the polymer (B1) may consist of (B1-a) or essentially up to 90 mol% or more, preferably up to 80 mol% or more.

[0049] The polymer (B1) can be prepared by direct polymerization from a monomer (B1-b) having a dicarboxylic acid group or a derivative thereof, such as maleic acid, fumaric acid, and derivatives thereof.

[0050] The polymer (B1) can also be prepared by grafting maleic anhydride onto the backbone of the polymer (B1) and hydrolyzing the anhydride to form two carboxylic acid groups.

[0051] Examples of suitable polymers (B1) include, for example, poly(butadiene-maleic acid) copolymer, propylene-maleic acid copolymer, ethylene-maleic acid copolymer, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, poly-maleic acid, poly(isobutylene-maleic acid) or hydrolysate thereof, ethylene-maleic anhydride copolymer or hydrolysate thereof, and combinations of two or more of these polymers.

[0052] Examples of suitable polymers (B1) in which carboxylic acid groups are grafted onto the backbone of the polymer (B1) include, for example, ethylene octene copolymer, ethylene butene copolymer, ethylene propylene copolymer, and maleic anhydride grafted onto a combination of two or more of these polymers.

[0053] Commercially available copolymers that can be used as the polymer (B1) of the present invention include ZeMac™ E60, E400 and Solution S67025 available from Vertellus and ISOBAM™ 104 available from Kuraray co., ltd.

[0054] Amino-silane (B2)

[0055] The amino-silane (B2) comprises a primary amine group and at least one hydroxyl group within the amino-silane molecule. The amino-silane (B2) used in the tie layer (B) is represented by the chemical formula I:

[0056] [Chemical Formula I]

[0057]

[0058] In chemical formula I, R 1 , R 2 and R 3 is independently selected from H, linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms. R 4 is H, and R 5 is H and -(CH2) y -Independently selected from NH2; x and y are integers independently selected from 1 to 6 (including boundary values). R 1 , R 2 and R 3 At least one of them is H. Preferably, R 1 , R 2 , R 3 , R 4 and R 5 is H, which is represented by the chemical formula II.

[0059] [Chemical Formula II]

[0060]

[0061] In Chemical Formula II, x is in the range of 1 to 6.

[0062] Non-limiting examples of suitable amino-silanes (B2) include 3-aminopropyltrimethoxysilane, 2-aminoethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminoethyltriethoxysilane and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and combinations of two or more of these aminosilanes.

[0063] Aminosilanes can be hydrolyzed in water to form oligomers. Such oligomers can be used in the present invention.

[0064] composition

[0065] As mentioned above, the tie layer (B) may be a reaction product of a polymer (B1) and an amino-silane (B2), or an unreacted mixture of these materials. During the preparation of the tie layer (B), a composition comprising (B1) a polymer containing carboxylic acid groups and (B2) an amino-silane containing a primary amine and at least one hydroxyl group is used. Suitable polymers (B1) and amino-silanes (B2) are described in detail above. The carboxylic acid groups of the polymer (B1) may be present as salts, for example, ammonium salts or alkali metal salts. The composition may further include a solvent, such as but not limited to water or an alcohol / water mixture, to form a solvent mixture. The composition may be an emulsion or dispersion containing the amino-silane material and the polymer, or the composition may be a solution.

[0066] The total concentration of the combination of at least one amino-silane (B2) and at least one polymer (B1) in the composition may be in the range of about 0.5 to 20 weight%, preferably 1 to 15 weight%, more preferably 1 to 10 weight% of the total concentration of the polymer (B1) and aminosilane (B2) based on the total weight of the composition.

[0067] The composition may further include a pH adjuster. Examples of pH adjusters include, for example, ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate and 1,8-diazabicyclo[5.4.0]undec-7-ene, salts of these materials, and mixtures of these materials and their salts. When the composition is a solution, the pH of the solution is preferably 5 to 14, more preferably 7 to 12, and even more preferably 8 to 11. Without being bound by theory, the carboxylic acid group of polymer (B1) is ionized in an alkaline solution, and thus polymer (B1) is considered stable in an alkaline solution. At the same time, the amino group of aminosilane (B2) is ionized in an alkaline solution. These two groups interact with each other in an alkaline solution, and thus the solution is considered stable when the solution is alkaline. When the solution is in a weak acid range (pH is 5 to 7), some of the carboxylic acid groups of the polymer (B1) are ionized, and thus the solution is also stable for the same reason discussed above.

[0068] The tie layer (B) may additionally include one or more additional components. Suitable additional components include, without limitation, reinforcing agents as described below for the polyamide composition (C), such as carbon black or glass fiber; other polymers, such as polyacrylate or ethylene acrylate copolymer; heat stabilizers as described below for the polyamide composition (C); and optional additives as described below for the polyamide composition (C).

[0069] If a solvent or one or more additional components are present in the tie layer (B), they are preferably present at a level of 50% by weight or more, or 20% by weight or more, or 15% by weight or more, or 10% by weight or more, based on the total weight of the composition. Complementarily, the amounts of polymer (B1) and aminosilane (B2) in the composition are 50% by weight or less, or 80% by weight or less, or 85% by weight or less, or 90% by weight or less, based on the total weight of the composition. The sum of the weight percentages of all components in the composition is 100% by weight. Alternatively, if an optional component is also suitable for use in the polymer composition (C), it may be present in the same amount suitable for use in the polyamide composition (C).

[0070] Manufacturing of the tie layer (B)

[0071] A tie layer (B) is formed on the metal (A).

[0072] Now, referring to the drawings, particularly FIG. 3, which show structures corresponding to similar reference numbers throughout the drawings, this composition can be applied onto a metal (A) (11) by any known method such as spraying, roll coating, or immersion, and then, if present, the solvent is evaporated (i.e., removed) to form a tie layer (B) (21) on the metal (A) (11). The evaporation of the solvent can be carried out at room temperature or under any suitable known conditions such as heating and atmospheric pressure or reduced pressure. Without being bound by theory, it is believed that the hydroxyl groups of the amino-silane interact with the hydroxyl groups on the surface of the metal when the composition is applied onto the metal (A) (11), and then the amino-silane binds to the surface of the metal (A) (11) by dehydration when the solvent is removed as shown in FIG. 3.

[0073] Now, referring to FIG. 2, the tie layer (B) (21) can be optionally heated to 100 to 300°C for, for example, 1 to 120 minutes after being applied to the metal (A) (11). Without being bound by theory, it is believed that when the tie layer (B) (21) is heated, two adjacent carboxylic acid groups of the polymer (B1) chemically react with the primary amine groups of the amino-silane (B2) to form cyclic imide groups that covalently bond the amino-silane molecules to the polymer molecules. Thus, if the heating step is added, the tie layer (B) (21) is believed to be the reaction product of the polymer (B1) and the amino-silane (B2), as shown in FIG. 2. However, this step may be omitted because the tie layer (B) (21) is heated during the lamination step of the polyamide (C) as described later.

[0074] The molar ratio (acid:amine) of two adjacent carboxylic acid groups in polymer (B1) to primary amine groups in amino-silane (B2) is 1:0.8 to 1:12, preferably 1:0.9 to 1:6, more preferably 1:0.9 to 1:5, even more preferably 1:1 to 1:4, and much more preferably 1:1.3 to 1:4. The molar ratios described herein are based on the fact that one anhydride group provides two carboxylic acid groups when hydrolyzed.

[0075] After the tie layer (B) (21) is formed on the metal (A) (11), the metal can be used as a stable metal part. The metal part having the tie layer (B) can be stored as a component ready to be laminated with polyamide (C), and can be distributed and used.

[0076] Polyamide composition (C)

[0077] The polyamide composition (C) may be of any shape, such as a sheet or plate, a tube or hose, or a box. If the polyamide composition (C) is a tube or hose, the end of the tube or hose may be placed in contact with the tie layer (B) on the metal (A). In other words, the polyamide metal laminate is not limited to a sheet or plate structure, but may be, for example, a polyamide hose bonded to a tie layer / metal part. Any article having a metal (A) bonded to the polyamide composition (C) through a tie layer (B) is within the scope of the present invention, regardless of the shape of the metal (A), the tie layer (B), or the polyamide composition (C), as long as it has a metal (A) / tie layer (B) / polyamide composition (C) structure in which a portion of the article is a continuous layer of (A), (B), and (C). More preferably, the metal (A) is in direct contact with the tie layer (B), the tie layer (B) is in direct contact with the polyamide composition (C), and the metal (A) and the polyamide composition (C) are in direct contact with the opposite surface of the tie layer (B).

[0078] Polyamide resin (C1)

[0079] The polyamide resin (C1) that can be used to manufacture the polyamide metal laminate described herein is not limited and may be any polyamide having a melting point greater than about 170°C, preferably greater than about 180°C. The polyamide is a condensation product of one or more dicarboxylic acids and one or more diamines, and / or a ring-opening polymerization product of one or more aminocarboxylic acids and / or one or more cyclic lactams. Suitable cyclic lactams are caprolactam and laurolactam. The polyamide may be completely aliphatic or semi-aromatic.

[0080] Examples of polyamides that can be used in polyamide-metal laminates include poly(tetramethylene hexanediamide) (PA46), poly(ε-caprolactam) (PA 6), poly(hexamethylene hexanediamide / (ε-caprolactam / )(PA 66 / 6), poly(hexamethylene hexanediamide) (PA 66), poly(hexamethylene hexanediamide / hexamethylene decandiamide) (PA66 / 610), poly(hexamethylene hexanediamide / hexamethylene dodecanediamide) (PA66 / 612), poly(hexamethylene hexanediamide / decamethylene decandiamide) (PA66 / 1010), poly(hexamethylene decandiamide) (PA610), poly(hexamethylene dodecanediamide) (PA612), poly(hexamethylene tetradecanediamide) (PA614), and poly(tetramethylene Hexanediamide / 2-Methylpentamethylene hexanediamide)(PA46 / D6), Poly(Tetramethylene hexanediamide / Tetramethylene terephthalamide)(PA46 / 4T), Poly(Tetramethylene hexanediamide / Hexamethylene terephthalamide)(PA46 / 6T), Poly(Tetramethylene hexanediamide / 2-Methylpentamethylene hexanediamide / Decamethylene terephthalamide)(PA46 / D6 / 10T), Poly(Hexamethylene hexanediamide / Hexamethylene terephthalamide)(PA66 / 6T), Poly(Hexamethylene hexanediamide / Hexamethylene isophthalamide / Hexamethylene terephthalamide (PA66 / 6I / 6T), Poly(Hexamethylene hexanediamide / 2-Methylpentamethylene hexanediamide / Hexamethylene Terephthalamide (PA66 / D6 / 6T), Poly(Tetramethylene Terephthalamide / Hexamethylene Hexanediamide) (PA4T / 66), Poly(Tetramethylene Terephthalamide / ε-Caprolactam) (PA4T / 6), Poly(Tetramethylene Terephthalamide / Hexamethylene Dodecanediamide) (PA4T / 612), Poly(Tetramethylene Terephthalamide / 2-Methylpentamethylene Hexanediamide / Hexamethylene Hexanediamide) (PA4T / D6 / 66), Poly(Hexamethylene Terephthalamide / 2-Methylpentamethylene Terephthalamide / Hexamethylene Hexanediamide) (PA6T / DT / 66), Poly(Hexamethylene Terephthalamide / Hexamethylene Hexanediamide) (PA6T / 66),Poly(hexamethylene terephthalamide / hexamethylene decandiamide)(PA6T / 610), Poly(hexamethylene terephthalamide / hexamethylene dodecanediamide)(PA6T / 612), Poly(hexamethylene terephthalamide / hexamethylene tetradecanediamide)(PA6T / 614), Poly(hexamethylene terephthalamide / isophoronediamine terephthalamide)(PA6T / IPDT), Poly(nonamethylene terephthalamide / nonamethylene decandiamide)(PA9T / 910), Poly(nonamethylene terephthalamide / nonamethylene dodecanediamide)(PA9T / 912), Poly(nonamethylene terephthalamide / 11-aminoundecanamide)(PA9T / 11), Poly(nonamethylene terephthalamide / 12-aminododecanamide)(PA9T / 12), Poly(Decamethylene Terephthalamide / 11-Aminoundecanamide)(PA 10T / 11), Poly(Decamethylene Terephthalamide / 12-Aminododecanamide)(PA10T / 12), Poly(Decamethylene Terephthalamide / Decamethylene Decandiamide)(PA10T / 1010), Poly(Decamethylene Terephthalamide / Decamethylene Dodecandiamide)(PA10T / 1012), Poly(Decamethylene Terephthalamide / Tetramethylene Hexanediamide)(PA10T / 46), Poly(Decamethylene Terephthalamide / ε-Caprolactam)(PA10T / 6), Poly(Decamethylene Terephthalamide / Hexamethylene Hexanediamide)(PA10T / 66), Poly(Dodecamethylene Terephthalamide / Dodecamethylene Includes dodecanediamide) (PA12T / 1212), poly(dodecamethylene terephthalamide / ε-caprolactam) (PA12T / 6), and poly(dodecamethylene terephthalamide / hexamethylene hexanediamide) (PA12T / 66).

[0081] The preferred polyamides disclosed herein include PA6T / DT, PA66, PA612, PA610, PA6T / 610, PA6T / 612, PA6T / IPDT, PA6, PA10, and blends thereof.

[0082] The amount of polyamide (C1) in the polyamide composition (C) is complementary to the amounts of other components in the polyamide composition (C). In other words, the sum of the weight percentages of all components in the polyamide composition (C) is 100 weight%. Thus, for example, if the polyamide composition (C) contains 70 weight% of reinforcing agent and 5 weight% of heat stabilizer based on the total weight of the polyamide composition (C), the amount of polyamide (C1) is 25 weight%.

[0083] Reinforcement agent (C2)

[0084] The polyamide composition (C) described herein may include one or more reinforcing agents (C2). The reinforcing agent is preferably selected from the group consisting of calcium carbonate, glass fibers having round and non-round cross-sections, glass flakes, glass beads, carbon fibers, aramid fibers, talc, mica, wollastonite, calcined clay, kaolin, diatomite, magnesium sulfate, magnesium silicate, barium sulfate, titanium dioxide, sodium aluminum carbonate, barium ferrite, potassium titanate, and mixtures of two or more suitable reinforcing agents (C2). In a preferred embodiment, the reinforcing agent is selected from the group consisting of glass fibers having a round cross-section, glass fibers having a non-round cross-section, and aramid fibers. The reinforcing agent may have a sizing agent or coupling agent, organic or inorganic material that improves the bonding between the reinforcing agent and the polyamide resin.

[0085] The polyamide composition (C) described herein may include one or more reinforcing agents in an amount of 0 to 70, preferably 10 to 70, most preferably 20 to 70 weight percent based on the total weight of all components in the polyamide composition (C).

[0086] Heat stabilizer (C3)

[0087] The polyamide composition (C) may include a heat stabilizer (C3). An organic heat stabilizer is preferred because inorganic heat stabilizers usually provide halogen ions and / or copper ions, which affect the corrosion of the metal (A).

[0088] The organic heat stabilizers disclosed herein, also referred to as antioxidants, include hindered phenolic compounds, amine-based heat stabilizers, and phosphorus-based heat stabilizers.

[0089] Examples of impaired phenolic compounds include tetrakis(methylene(3,5-di-(tert)-butyl-4-hydroxyhydrocinnamate))methane, commercially available as Irganox™ 1010 from CIBA Specialty Chemicals, Tarrytown, New York, USA, and N,N'-hexamethylenebis(3,5-di-(tert)butyl-hydroxyhydro-cinnamamide), also available as Irganox™ 1098 from CIBA Specialty Chemicals. Other suitable hindering phenols include 1,3,5-trimethyl-2,4,6-tris(3,5-di-(tert)-butyl-4-hydroxybenzyl)benzene and 1,6-hexamethylenebis(3,5-di-(tert)butyl4-hydroxyhydrocinnamate), both of which are available from CIBA Specialty Chemicals as Irganox™ 1330 and 259, respectively.

[0090] Examples of amine-based heat stabilizers include hindered amine light stabilizers (HALS). Preferably, HALS are compounds derived from substituted piperidine compounds, specifically alkyl-substituted piperidyl, piperidinyl, or piperazinone compounds, and any compounds derived from substituted alkoxypiperidinyl compounds. Examples of such compounds are as follows: 2,2,6,6-tetramethyl-4-piperidone; 2,2,6,6-tetramethyl-4-piperidinol; bis-(1,2,2,6,6-pentamethylpiperidyl)-(3',5'-di-tert-butyl-4'-hydroxybenzyl)butylmalonate; di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770, MW 481); Oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin® 622); oligomer of cyanuric acid and N,N-di(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine; bis-(2,2,6,6-tetramethyl-4-piperidinyl) succinate; bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin® 123); bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (Tinuvin® 765); Tinuvin® 144; Tinuvin® XT850; Tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate; N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexane-1,6-diamine (Chimasorb® T5); N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; 2,2'-[(2,2,6,6-tetramethyl-piperidinyl)-imino]-bis-[ethanol]; poly((6-morpholine-S-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino) (Cyasorb® UV 3346); 5-(2,2,6,6-tetramethyl-4-piperidinyl)-2-cyclo-undecyl-oxazole) (Hostavin® N20);1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetramethyl-piperazinone); 8-acetyl-3-dotesyl-7,7,9,9-tetramethyl-1,3,8-triazspiro(4,5)decane-2,4-dione; polymethylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)-piperidinyl]siloxane (Uvasil® 299); 1,2,3,4-butane-tetracarboxylic acid-1,2,3-tris(1,2,2,6,6-pentamethyl-4-piperidinyl)-4-tridecyl ester; copolymer of alpha-methylstyrene-N-(2,2,6,6-tetramethyl-4-piperidinyl) maleimide and N-stearyl maleimide; Polymer of 1,2,3,4-butanetetracarboxylic acid, beta,beta,beta',beta'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, and 1,2,2,6,6-pentamethyl-4-piperidinyl ester (Mark® LA63); polymer of 1,2,3,4-butanetetracarboxylic acid, and 2,2,6,6-tetramethyl-4-piperidinyl ester, 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, beta,beta,beta',beta'-tetramethyl-polymer (Mark® LA68); D-glucitol, 1,3:2,4-bis-O-(2,2,6,6-tetramethyl-4-piperidinylidene)-(HALS 7); 7-oxa-3,20-diazadisspiro[5.1.11.2]-heneichosan-21-one-2,2,4,4-tetramethyl-20-(oxiranylmethyl) oligomer (Hostavin® N30); propanedioic acid, [(4-methoxyphenyl)methylene]-,bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Sanduvor® PR 31); Formamide, N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl (Uvinul® 4050H); 1,3,5-triazine-2,4,6-triamine, N,N'"-[1,2-ethandiylbis [[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl]]-bis[N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)(Chimassorb® 119 MW 2286);Poly [[6-[(1,1,3,33-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)-imino]-1,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl)imino]](Chimassorb® 944 MW 2000-3000); 1,5-dioxaspiro (5,5)undecane 3,3-dicarboxylic acid, bis(2,2,6,6-tetramethyl-4-peridinyl) ester (Cyasorb® UV-500); 1,5-Dioxaspiro (5,5) Undecane 3,3-Dicarboxylic acid, bis(1,2,2,6,6-Pentamethyl-4-Peridinyl) Ester (Cyasorb® UV-516); N-2,2,6,6-Tetramethyl-4-Piperidinyl-N-Amino-Oxamide; 4-Acryloyloxy-1,2,2,6,6-Pentamethyl-4-Piperidine, 1,5,8,12-Tetrakis[2',4'-Bis(1",2",2",6",6"-Pentamethyl-4"-Piperidinyl(Butyl)amino)-1',3',5'-Triazine-6'-yl]-1,5,8,12-Tetraazadodecane; HALS PB-41 (Clariant Huningue SA); Nylostab® S-EED (Clariant Huningue SA); 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidine-2,5-dione; Uvasorb® HA88; 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetramethyl-piperazinone)(Good-rite® 3034); 1,1'1"-(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethandiyl)tris(3,3,5,5-tetramethylpiperazinone) (Good-rite® 3150) and; 1,1',1"-(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethandiyl)tris(3,3,4,5,5-tetramethylpiperazinone) (Good-rite® 3159). (Tinuvin® and Chimassorb® materials are available from Ciba Specialty Chemicals; Cyasorb® materials are available from Cytec Technology Corp.;Uvasil® materials are available from Great Lakes Chemical Corp.; Saduvor®, Hostavin®, and Nylostab® materials are available from Clariant Corp.; Uvinul® materials are available from BASF; Uvasorb® materials are available from Partecipazioni Industriali; and Good-rite® materials are available from BF Goodrich Co. Mark® materials are available from Asahi Denka Co.

[0091] Other specific HALS include di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770, MW 481) Nylostab® S-EED (Clariant Huningue SA); 1,3,5-triazine-2,4,6-triamine, N,N'"-[1,2-ethandiylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl]]-bis[N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)(Chimassorb® 119 MW 2286); and poly[[6-[(1,1,3,33-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)-imino]-1,6-hexanediyl It is selected from the group consisting of [(2,2,6,6-tetramethyl-4-piperidinyl)imino]](Chimassorb® 944 MW 2000-3000).

[0092] The concentration of the optional heat stabilizer in the polyamide composition (C), when present, is in the range of about 0.01 to 5, preferably 0.1 to 4, more preferably 0.1 to 2 weight percent based on the total weight of all components in the polyamide composition (C).

[0093] additives

[0094] Optional additives that may be added to the polyamide composition (C) include, for example, waxes, UV stabilizers, colorants, lubricants, and mixtures thereof. Optional additives may also include materials that, when added to the polyamide composition (C) described herein, produce a polyamide composition (C) having a linear coefficient of thermal expansion similar to that of the metal used. For aluminum, an example of such an additive is an aramid fiber, such as DuPont™ Kevlar® aramid fiber.

[0095] The concentration of the additive in the polyamide composition (C), when present, is in the range of about 0.01 to 25, preferably 0.1 to 20 weight%, based on the total weight of all components in the polyamide composition (C).

[0096] Manufacture of polyamide metal laminates

[0097] The polyamide-metal laminates described herein can generally be manufactured by the following steps:

[0098] a) a step of forming a tie layer on a metal to provide a metal / tie layer laminate;

[0099] b) A step of bonding the metal / tie layer laminate from step a) to a polyamide composition to provide a polyamide metal laminate.

[0100] Step a) is the same as described above as an explanation for forming a tie layer (B) on the metal (A). As mentioned, the heating step of the tie layer (B) is optional. Without being bound by theory, it is believed that the carboxylic acid group or carboxylic acid diad of the polymer (B1) reacts with the amino-silane (B2) when the tie layer (B) is heated.

[0101] There are several feasible methods for step (b). A suitable first method is to pre-manufacture a molded polyamide and then bond it to the surface of the tie layer prepared by step (a). This method is also referred to as welding (method). Specifically, the polyamide metal laminate can be manufactured by the following procedure.

[0102] The polyamide composition (C) may be formed using any procedure such as molding, extrusion, or compression to provide the polyamide composition (C) in a desired shape, such as a tube or hose. The formed polyamide composition (C) is placed in contact with a metal-tie layer laminate as disclosed herein. While the polyamide composition (C) and the metal-tie layer laminate are in contact with each other, the polyamide resin (C1) is preferably melted and heated under pressure to a temperature of 200 to 350°C for a period sufficient to allow the reaction between the polyamide amine groups and the acid groups of the tie layer (B). For example, any welding method using heating equipment, such as an oven or hot plate, laser welding, ultrasonic welding, and hot gas welding may be used. Exemplary conditions for the hot press are 220 to 320°C for 1 to 120 seconds at 0.1 MPa or higher. Subsequently, if used, the pressure is released to obtain an article comprising the polyamide-metal laminate.

[0103] A suitable second method is to supply a polyamide composition comprising polyamide (C1) and optionally a reinforcing agent (C2) and a heat stabilizer (C3) to an injection molding machine, melt-mix to form a polyamide composition (C), and then mold the polyamide composition (C) directly onto the surface of a metal-tie layer laminate, preferably by injection molding. Without being bound by theory, it is assumed that the polyamide (C1) melts during the injection of the polyamide composition (C). Accordingly, it is further assumed that the temperature of the tie metal laminate and the injected polyamide composition (C) is sufficiently high to react the amine groups of the polyamide (C1) with the acid groups of the tie layer (B).

[0104] When a polyamide composition (C) is bonded to a metal (A) using a tie layer (B), the resulting polyamide-metal laminate exhibits a combination of excellent hydrolytic resistance as well as desirable bonding strength between the polyamide composition (C) and the metal (A). Without being bound by theory, it is believed that the amine terminal groups of the polyamide bond to the carboxylic acid groups of the polymer, providing imide groups that connect or chemically bond the polyamide molecules to the tie layer.

[0105] polyamide-metal laminate

[0106] Polyamide-metal laminates obtained by bonding via a specific tie layer exhibit not only desirable bond strength, which is greater than that of laminates using a conventional surface treatment (aminopropyl silane), but also excellent hydrolytic resistance. In particular, polyamide-metal laminates using the tie layer of the present invention exhibit desirable hydrolytic resistance when exposed to ethylene glycol / aqueous solution for 1,000 hours at 130°C, compared to the initial bond strength before exposure to ethylene glycol / aqueous solution. Referring to FIG. 1, the expected structure for the polyamide-metal laminate of the present invention is illustrated. Without being bound by theory, the tie layer ( 21The silanol group of ) is a metal (e.g., aluminum)( 11 While reacting with the hydroxyl groups of ), the tie layer ( 21 The two carboxylic acid groups of ) are polyamide compositions ( 31 It is believed to form a cyclic imide structure with the nitrogen atom of the amino group. Therefore, aluminum ( 11 ) and polyamide composition ( 31 ) is the Thai layer ( 21 It is strongly bonded by ). On the other hand, when using a conventional surface treatment such as aminopropyl silane as shown in FIG. 5, the polyamide composition ( 31 The interaction between the carboxylic acid group of ) and the amino group of amino-silane is weak, particularly in the presence of water (hydrolysis). Figure 4 shows another comparative model when amino-silane is not included in the tie layer. Polyamide composition ( 31 ) is a polymer( 23 It can be combined with ), but the polymer ( 23 ) carboxylic acid and aluminum( 11) The interaction of the hydroxyl group is weak, and therefore aluminum ( 11 ) and polyamide composition ( 31 Desirable bond strength can be obtained between ).

[0107] article

[0108] Articles of the present invention comprise the polyamide-metal laminate disclosed above. Articles may be used in any technology requiring direct bonding of metal to polyamide. Examples of such technologies include the automotive, electronics, and construction industries. In particular, articles are useful for tubes, hoses, water pump housings, oil filter housings, and transmission housings in automotive technology.

[0109] The following examples are provided to further explain the invention. These examples, representing preferred embodiments currently being considered for carrying out the invention, are intended to illustrate the invention and are not intended to limit it.

[0110] Examples

[0111] In the table below, the article that is an embodiment of the present invention is identified as "E", and in the table below, the comparative example is identified as "C".

[0112] ingredient

[0113] In the compounds, processes, and articles exemplified in the table below, the following materials were used. All percentages are by weight unless otherwise indicated.

[0114] metal layer (A)

[0115] Metal 1: Aluminum comprising 1.2 to 0.8 weight% magnesium, 0.7 weight% iron, 0.4 to 0.8 weight% silica, and 1.4 weight% or less of other metals, which is available as JIS (Japanese Industrial Standard) A6061.

[0116] Metal 2: Aluminum comprising 2.2 to 2.8 weight% magnesium and 1.3 weight% or less of other metal, which is available as JIS A5052.

[0117] Metal 3: Aluminum containing more than 99.5 weight% aluminum and 0.5 weight% or less of other metals, which is available as JIS A1050.

[0118] Polymer (B1)

[0119] Polymer A: An ethylene maleic anhydride copolymer available from Vertellus Specialties Inc. as ZeMac E60, reported as a 1:1 alternating copolymer of ethylene and maleic anhydride.

[0120] Polymer B: Polybutadiene-maleic acid copolymer available from Polysciences, Inc. as a 42% solid poly(butadiene-maleic acid) in water.

[0121] Amino silane (B2)

[0122] Silane A: A 30% by weight aqueous solution of 3-aminopropyltrimethoxysilane hydrolysate available from ShinEtsu Silicone as KBP-90.

[0123] Silane B: An amino-silane coupling agent comprising N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, available from ShinEtsu Silicone as KBM-603.

[0124] Silane C: An amino-silane coupling agent comprising 3-aminopropyltriethoxysilane, available from ShinEtsu Silicone as KBE-903.

[0125] Silane D: A 30% by weight aqueous solution of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane hydrolysate available from ShinEtsu Silicone as KBP-64.

[0126] Polyamide composition (C)

[0127] Polyamide A (PA-A): comprising 51% PA66, 13% PA6, 35 wt% glass fiber, and an organic heat stabilizer, wherein PA66 has a melting point of 260°C and PA6 has a melting point of 221°C.

[0128] Polyamide B (PA-B): a polyamide composition comprising 66% PA66 and 33% glass fiber, not comprising a heat stabilizer, wherein PA66 has a melting point of 260°C.

[0129] Polyamide C (PA-C): a polyamide composition comprising 66% PA612, 33% glass fiber and an organic heat stabilizer, wherein PA612 has a melting point of 218°C.

[0130] Polyamide D (PA-D): a polyamide composition comprising 65% PA612 and 33% glass fiber, not comprising a heat stabilizer, wherein PA612 has a melting point of 218°C.

[0131] Polyamide E (PA-E): a polyamide composition comprising 63% PA6T / DT, 35% glass fiber and an organic heat stabilizer, wherein PA6T / DT has a melting point of 300°C.

[0132] Heat stabilizer (C3)

[0133] HS2-A: An organic heat stabilizer comprising a mixture of 0.3% Chimasorb 944FDL, 0.75% Irganox1098, and 0.3% Ultranox626A (wherein the weight is based on the weight of the polyamide composition (C)).

[0134] HS2-B: An organic heat stabilizer available from BASF as Irganox® 1098.

[0135] Before treating aluminum with the metal treatment solution disclosed herein, the aluminum surface may be cleaned by one of the following cleaning procedures:

[0136] Cleaning procedure

[0137] Procedure A - Expose the aluminum surface to isopropyl alcohol.

[0138] Procedure B - Polish the aluminum surface with an abrasive material (sandpaper with 500 grit) to provide a polished aluminum surface, then expose the aluminum surface to a cleaning solution, and subsequently rinse the treated aluminum surface with a detergent solution to remove any remaining cleaning solution.

[0139] Procedure C - The aluminum surface is blasted with aluminum oxide particles (#240) at 0.2 MPa using Baby-Blast manufactured by Macoho Co., Ltd.

[0140] Procedure D - 14 mW / cm² for 1 hour at room temperature (26℃) at a distance of 5 cm 2irradiate with ultraviolet light (254 nm).

[0141] Welding A (Hot Press Welding)

[0142] Now, referring to FIG. 6, the polyamide cap (41) has a cylindrical cross-section in a horizontal plane perpendicular to the vertical plane in which the cross-section of the polyamide cap (41) is shown. This cylindrical cross-section is the welding area (42) where the polyamide cap (41) will be attached to the metal layer (A). Now, referring to FIG. 7, the aluminum test plate (43) (50 mm square and 6 mm thick) has a circular hole (25 mm) in the center. The aluminum test plate (43) is cleaned and then treated with a metal treatment solution to create a tie layer (44) on the metal surface. The polyamide cap test sample (41) is placed in the center in contact with the aluminum plate (43) so that the polyamide cap (41) covers the circular hole. The surface area (42) of the polyamide cap (41) in contact with the aluminum plate (43) is approximately 177 mm² 2 The aluminum plate (43) and cap (41) were placed on a hot plate (46) while a metal cylinder (45) transmitting pressure was placed directly above the welding area (42). The direction of the pressure is indicated by an arrow. After hot-pressing this assembly at 240 to 315°C under 0.3 MPa for 1 minute, it was cooled to a temperature lower than the melting temperature of the polyamide composition (C) under the same pressure.

[0143] Welding B (Direct Injection Molding)

[0144] Now, referring to FIG. 9, an aluminum plate (50) with a width of 18 mm, a length of 45 mm, and a thickness of 2.0 mm was used as an aluminum test plate. The aluminum plate (50) was cleaned and then treated with a metal treatment solution to deposit a tie layer (B) on the aluminum plate (50). After placing the aluminum plate (50) on a molding tool, a polyamide molding (51) with a width of 10 mm, a length of 45 mm, and a thickness of 3 mm was formed on the aluminum plate (50) by direct molding with a 10 x 5 mm overlapping area (52). In the case of polyamide, the set cylinder temperature is 280 to 300°C and the tool temperature is 120 to 160°C. Direct injection molding was performed using the heating and cooling system "Y-HeaT" from Yamashita Electric Co., Ltd., the heating temperature was 240℃, the cooling temperature was 180℃, the holding pressure was 40 MPa, and the holding time was 6 seconds.

[0145] Bond strength retention rate test

[0146] Two test specimens were prepared for each polyamide composition and surface treatment solution. One test specimen was exposed to an aqueous ethylene glycol solution heated at 130°C for 1,000 hours (unless otherwise specified) to observe hydrolytic resistance, while the second test specimen was not exposed to the solution. The bonding strength of both test specimens was measured.

[0147] After exposing the test specimen to a heated aqueous ethylene glycol solution, the bond strength of the formed polyamide composition to the aluminum plate was tested. Referring now to FIG. 8, for weld (A), the cap-formed polyamide (41) was pushed out from the inner face of the cap by a piston (48) having a shaft 32 mm long and 8 mm in diameter. The arrow indicates the direction of the applied force. The metal plate (47) is held in place with the metal cylinder (49) until the polyamide cap (41) is completely separated from the plate (47). For weld (B), the test specimen was held in a specimen retainer based on the retainer shown in FIG. 1 of ISO 19095-3, § 5.2.1.2. Measurements were taken at a crosshead speed of 10 mm / min until fracture. The fracture load (N) was calculated based on the bond area (mm²). 2 The shear stress (MPa) was calculated by dividing by ). The maximum force required to separate the molded polyamide composition from the aluminum plate is the bond strength of the test specimen. The bond strength of the test specimen not exposed to the aqueous ethylene glycol solution is compared with the bond strength of the test specimen prepared by the same process but exposed to the aqueous ethylene glycol solution. The difference between the bond strength of the test specimen after exposure to the aqueous ethylene glycol solution and the bond strength of the test specimen not exposed to the aqueous ethylene glycol solution represents the bond strength retention rate of the test specimen.

[0148] Table 1 shows the composition of the polyamide layer used in the examples and comparative examples. Table 2 shows the composition of the solvent solution used to apply the tie layer (B) to the aluminum before bonding the aluminum to the polyamide layer. In Tables 1 and 2, the values ​​are weight percentages based on the total weight of the polyamide composition in Table 1 and the total weight of the metal treatment solution in Table 2. Bond strength retention values ​​for various test specimens are shown in Tables 3 and 4.

[0149] [Table 1]

[0150]

[0151] [Table 2]

[0152]

[0153] [Table 3]

[0154]

[0155] Table 3 shows that the tie layer improves the hydrolytic resistance between the molded polyamide composition and aluminum. Also refer to the results obtained for Comparative Example C10 below. When using aliphatic polyamides, a desirable bond strength retention rate is obtained. PA 66 or a blend of PA66 and PA6 is used for E1 and E2, respectively. PA612 is used for E3 and E4. E5 uses a semi-aromatic polyamide, PA6T / DT, and articles made from these polyamides using the tie layer disclosed herein also exhibit desirable bond strength retention rate characteristics.

[0156] Table 3 also shows the effect of various heat stabilizers on the bond strength retention rate of the polyamide composition to aluminum. These examples (E1 to E7) show that the resulting bond strength retention rate between the molded polyamide composition and aluminum after exposure of the article to an ethylene glycol / aqueous solution at 130°C for 1000 hours is at least 7.1%.

[0157] [Table 4]

[0158]

[0159] Table 4 shows the effect of the ratio of amino-silane material to polymer on the bond strength retention rate in the metal treatment solution. In C8, the ratio of amino-silane material to polymer is about 1 to 14.4, which is outside the desired range of 1 to 0.8 to 1 to 12, and thus a bond strength retention rate of less than 1% is obtained.

[0160] Table 4 also shows how effective solvent solutions containing various amino-silane materials and polymers are in the retention rate of bond strength of molded polyamide compositions to aluminum of such metal treatment solutions. The solvent solution of E11 contains a polybutadiene-maleic acid copolymer. This solvent solution provides a desirable retention rate of bond strength between aluminum and the molded polyamide composition, which demonstrates that the solvent solutions described herein can be prepared using both acid and anhydride copolymers.

[0161] The solvent solution used in C10 does not contain a polymer. The solvent solution used in C11 does not contain an amino-silane material. In both comparative examples, the desired bond strength retention rate is not obtained. C12 contains N-2-(aminoethyl)-3-aminopropyltrimethoxysilane as the amino-silane material, and the resulting article does not exhibit the desired bond strength retention rate.

[0162] C9 shows the effect of the ratio of amino-silane material to polymer on the bond strength retention rate in a metal treatment solution. In C9, the ratio of amino-silane material to polymer is about 5.8 to 1, which is outside the desired range of 3 to 1 to 0.8 to 8, and thus a bond strength retention rate of less than 1% is obtained.

[0163] [Table 5]

[0164]

[0165] Table 5 shows the effects of different cleaning methods and welding processes (direct injection molding). Referring to Examples 13, 14 and Comparative Example 13, cleaning procedure A does not achieve excellent bond strength. Referring to Example 15, the polyamide-metal laminate formed by direct injection molding (welding B) exhibits the same excellent hydrolytic resistance as the sample formed by hot press molding (welding A).

[0166] Surface analysis of aluminum plates

[0167] After performing the cleaning process, the surface of the aluminum plate was analyzed by XPS or TOF-SIMS. Procedure B or D disclosed above was selected. The plate for Comparative Example 14 (C14) was cleaned by procedure B and then wiped with a cloth soaked in oil. After surface analysis, polyamide was laminated in the same manner as in Example 1. Bond strength and hydrolytic resistance were analyzed.

[0168] XPS measurements from PHI co., inc. QuanteraSXM, X-ray source: Al (1486.6 eV), detection area: Ø 100 micrometers, detection depth: 4 to 5 nm, measurement mode: wide scan: Al2p, O1s, C1s, and the percentage of each elemental signal was determined by curve fitting of the peak area.

[0169] TOF-SIMS: Machine: TOF.SIMS5-300 from IONTOF GmbH, Test Conditions: Primary Ion: Bi, Analysis Area: 300 micrometers. Mass Spectrometer: Time-of-Flight Mass Spectrometer, each mass fragment of Al, Al(OH)3, Al2O3, or AlO(OH) n It was determined by comparing with a standard sample of H2O data.

[0170] [Table 6]

[0171]

[0172] Table 6 shows the effects of aluminum surface conditions. Referring to E16 and C14, oil contamination reduces bond strength even after the same surface cleaning B. Referring to C15 and E18, surface cleaning such as polishing and UV / ozone treatment is required for excellent bond strength, and these effects are achieved by TOF-SIMS using Al(OH)3 or partially aluminum hydroxide compounds, such as AlO(OH) n It may also be detected by fragments of H2O.

[0173] [Table 7]

[0174]

[0175] [Table 8]

[0176]

[0177] To further clarify the molar ratio of the amino-silane material and polymer, the retention rate of bond strength was measured in several solvent solutions after exposing an article manufactured by hot press welding (welding B) of molded polyamide (PA66) and aluminum to an ethylene glycol / aqueous solution at 130°C for 250 hours.

[0178] Table 7 shows how much the solvent solution contains amino-silane material and ethylene maleic acid copolymer in varying ratios.

[0179] In E18 to E27, the ratio of amino-silane material to polymer is about 1 to 19, which produces a desired initial bond strength of more than 50 MPa.

[0180] In addition, in E19 to E24, the molar ratio of amino-silane to polymer is about 1:1.3 to 1:4, and the article exhibits an excellent bond strength retention rate of at least 20 MPa after exposure to ethylene glycol / aqueous solution at 130°C for 250 hours.

[0181] [Table 9]

[0182]

[0183] Table 9 shows the weld strength after exposure to 90°C water for 96 hours. E28, using SS-21 containing polymer D, a diamine-type hydrolysate of amino-silane, and polymer A, exhibited excellent bond strength, whereas C17, using SS-8 consisting only of amino-silane, showed 0 MPa after exposure. It can be seen that the diamine-type of amino-silane having terminal -NH2 groups can also be effective in achieving excellent hydrolytic resistance when hydrolyzed.

[0184] Although specific preferred embodiments of the present invention have been described and specifically illustrated above, the present invention is not limited to such embodiments. Rather, while many features and advantages of the present invention, along with details of the structure and function of the present invention, have been presented in the foregoing description, the present disclosure is merely illustrative, and it should be understood that specific modifications to the shape, size, and configuration of parts may be made within the principles of the present invention, extending to the full scope of the broad general meaning of the terms expressed in the appended claims.

Claims

Claim 1 A polyamide-metal laminate comprising (A) a metal, (B) a tie layer formed on the surface of the metal, and (C) a polyamide composition formed on the surface of the tie layer, wherein the tie layer comprises B1) a polymer comprising carboxylic acid groups; and B2) an amino-silane comprising a primary amine and at least one hydroxyl group, wherein at least two carboxylic acid groups in the polymer (B1) are adjacent to each other, and the molar ratio of two adjacent carboxylic acid groups in the polymer (B1) to the primary amine group in the amino-silane (B2) is 1:0.8 to 1:

12. Claim 2 A polyamide-metal laminate according to claim 1, wherein the content of two adjacent carboxylic acid groups in the polymer (B1) is 2 weight% or more based on the total weight% of the polymer (B1). Claim 3 A polyamide-metal laminate according to claim 1 or 2, wherein the polymer (B1) comprises one or more polymers selected from the group consisting of poly(butadiene-maleic acid) copolymer, propylene-maleic acid copolymer, ethylene-maleic acid copolymer, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, polymaleic acid(s), maleic anhydride-grafted ethylene octene copolymer, maleic anhydride-grafted ethylene butene copolymer, and maleic anhydride-grafted ethylene propylene copolymer. Claim 4 In claim 1 or 2, the amino-silane (B2) is a polyamide-metal laminate represented by the formula I: [Formula I] (during food, R 1 , R 2 and R 3 is independently selected from H, C1 to C6 linear, branched, or cyclic alkyl groups; and R 4 is H and; R 5 is H and -(CH2) y Independently selected from -NH2; x and y are independently in the range of 1 to 6; R 1 , R 2 and R 3 At least one of them is H). Claim 5 A polyamide-metal laminate according to claim 1 or 2, wherein the metal (A) is aluminum. Claim 6 In paragraph 5, the aluminum is a polyamide-metal laminate having hydroxyl groups on the surface of the aluminum. Claim 7 A metal part having a tie layer on the surface of the metal part, wherein the tie layer comprises B1) a polymer comprising carboxylic acid groups; and B2) an amino-silane comprising a primary amine and at least one hydroxyl group, wherein at least two carboxylic acid groups in the polymer (B1) are adjacent to each other, and the molar ratio of the carboxylic acid groups in (B1) to the primary amine groups in (B2) is 1:0.8 to 1:

12. Claim 8 A composition suitable for laminating a polyamide onto a metal surface, wherein the composition comprises (b-1) a polymer containing a carboxylic acid group, (b-2) an amino-silane containing a primary amine and at least one hydroxyl group, and (b-3) water, wherein at least two carboxylic acid groups in the polymer (b-1) are adjacent to each other, and the molar ratio of the carboxylic acid groups in (b-1) to the primary amine groups in (b-2) is 1:0.8 to 1:

12. Claim 9 A composition according to claim 8, wherein the pH is 5 or higher. Claim 10 A method for laminating polyamide on the surface of aluminum, comprising: (i) preparing aluminum in which the surface of the aluminum has been cleaned; (ii) forming a tie layer on the surface of the aluminum by applying the composition of claim 8; and (iii) laminating a polyamide composition on the tie layer under heating at a temperature at least for melting polyamide. Claim 11 Article comprising the polyamide-metal laminate of claim 1 or 2. Claim 12 Article 11, selected from the group consisting of tubes, hoses, water pump housings, oil filter housings and transmission housings.

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