阅读说明：本技术 聚酰胺组合物及其镀敷应用 (Polyamide composition and plating application thereof ) 是由 K·M·怀特 S·E·波尔斯 J·G·雷 B·J·司帕克斯 于 2019-06-27 设计创作，主要内容包括：本公开涉及聚酰胺组合物和所得注射成型制品,所述制品可镀,例如可金属涂布,以形成结构上美观的注射成型制品。所述聚酰胺组合物可包括40重量％至80重量％的聚酰胺、0.5重量％至40重量％的可蚀刻填料、5重量％至30重量％的玻璃纤维、任选小于40重量％的半结构矿物和任选0.1重量％至13重量％的添加剂。所述聚酰胺组合物赋予注射成型制品极好的表面外观和优异的机械性质以使其基本没有视觉缺陷。(The present disclosure relates to polyamide compositions and resulting injection molded articles that can be plated, e.g., metal coated, to form injection molded articles that are structurally aesthetic. The polyamide composition may include 40 to 80 weight percent polyamide, 0.5 to 40 weight percent etchable filler, 5 to 30 weight percent glass fiber, optionally less than 40 weight percent semi-structural mineral, and optionally 0.1 to 13 weight percent additives. The polyamide composition imparts excellent surface appearance and excellent mechanical properties to injection molded articles so that they are substantially free of visual defects.)

1. A polyamide composition comprising:

40 to 80 weight percent of a polyamide;

0.5 to 40 weight percent of an etchable filler;

5 to 30 wt% of glass fibers having an average diameter of at most 10 microns;

less than 40% by weight of semi-structural minerals; and

0.1 to 13% by weight of additives.

2. A composition according to claim 1, wherein the polyamide comprises PA-6, PA4,6, PA-6,9, PA-6,10, PA-6,12, PA11, PA12, PA9,10, PA9,12, PA9,13, PA9,14, PA9,15, PA-6,16, PA9,36, PA10,10, PA10,12, PA10,13, PA10,14, PA12,10, PA12,12, PA12,13, PA12,14, PA-6,13, PA-6,15, PA-6,16, PA-6,13, PAMXD,6, PA4T, PA5T, PA-6T, PA10T, PA12T, PA4, PA5, PA-T, PA-6, T, a terpolymer and mixtures thereof.

3. The composition according to any of claims 1 or 2, wherein the polyamide is a copolymer comprising PA-6,6 and PA-6I, wherein PA-6I is from 2 to 20 wt%.

4. The composition according to any one of claims 1 or 2, wherein the polyamide is a terpolymer comprising PA-6, PA-6 and PA-6I, wherein the terpolymer comprises 2 to 20 wt% PA-6I and 2 to 20 wt% PA-6.

5. The composition according to any one of claims 1-4, wherein the additive comprises at least one of: inorganic stabilizers, organic stabilizers, flame retardants, lubricants, dyes, pigments, nucleating agents, metal flakes, impact modifiers, antistatic agents, conductivity additives, mold release agents, optical brighteners, adhesion promoters, aging inhibitors, antioxidants, antiozonants, light stabilizers, ultraviolet absorbers, ultraviolet blockers, inorganic heat stabilizers, organic heat stabilizers, processing aids, crystallization promoters, crystallization retarders, flow aids, fibrous materials, and particulate fillers.

6. The composition according to any one of claims 1-5, wherein the additive comprises 1 to 10 wt% of a pigment, 0.05 to 1 wt% of a lubricant, and/or 0.25 to 2 wt% of a processing aid, wherein the pigment comprises a thermally stable nigrosine, wherein the lubricant comprises zinc stearate, and wherein the processing aid comprises a substituted piperidine compound.

7. The composition of any of claims 1-6, wherein the polyamide composition comprises 0.5 wt% to 25 wt% etchable filler, and wherein etchable filler is coated with one or more of an organosilane coating, a vinylsilane coating, or an aminosilane coating.

8. The composition according to any one of claims 1-7, wherein the etchable filler comprises one or more of magnesium hydroxide, calcium carbonate, and wollastonite.

9. The composition according to any of claims 1-8, wherein the glass fibers have an average diameter of 4 microns to 8 microns.

10. The composition according to any one of claims 1-9, wherein the composition comprises a semi-structural mineral, wherein the semi-structural mineral comprises one or more of kaolin, mica, talc and wollastonite.

11. The composition according to any one of claims 1-10, wherein the composition has an image distinctness of greater than 50 as measured by a Byk Gardner Wave Scan meter, and wherein the composition has an R-value of greater than 5 as measured by a Byk Gardner Wave Scan meter.

12. The composition according to any one of claims 1-11, wherein the composition has 1.25g/cm³To 1.6g/cm³And wherein the composition has a melting point of 220 ℃ to 260 ℃.

13. The composition according to any of claims 1-3 and 5-12, wherein the polyamide is a copolymer comprising PA-6,6 and PA-6I, wherein the composition comprises glass fibers having an average diameter of 4 microns to 8 microns, wherein the composition has 1.3g/cm³To 1.6g/cm³Wherein the composition has an image distinctness of greater than 65 as measured by a Byk Gardner Wave Scan instrument, wherein the composition has an R value of greater than 7 as measured by a Byk Gardner Wave Scan instrument.

14. The composition according to any one of claims 1,2, and 4-12, wherein the polyamide is a terpolymer comprising PA-6, PA-6I, and PA-6, wherein the composition comprises glass fibers having an average diameter of 4 microns to 8 microns, wherein the composition has 1.3g/cm³To 1.6g/cm³Wherein the composition has an image distinctness of greater than 65 as measured by a Byk Gardner Wave Scan instrument, wherein the composition has an R value of greater than 7 as measured by a Byk Gardner Wave Scan instrument.

15. An injection molded article formed from the composition of any of claims 1-14, wherein the injection molded article is metal plated, the metal comprising one or more of copper, manganese, tin, nickel, iron, chromium, zinc, gold, platinum, cobalt, phosphorus, aluminum, and alloys thereof.

16. A polyamide composition comprising:

40 to 80 weight percent of a polyamide;

0.5 to 40 weight percent silane coated magnesium hydroxide;

5 to 30 wt% of glass fibers having an average diameter of at most 10 microns;

less than 40% by weight kaolin; and

0.1 to 13% by weight of additives.

17. The composition according to claim 16, wherein the additive comprises 0.5 to 10 wt% of thermally stable nigrosine, 0.05 to 1 wt% of zinc stearate, and/or 0.25 to 2 wt% of a substituted piperidine compound.

18. A method of making an injection molded article comprising:

provided is a polyamide composition comprising: 40 to 80 weight percent of a polyamide; 0.5 to 40 weight percent of an etchable filler; 5 to 30 weight percent glass fibers, wherein the glass fibers have an average diameter of at most 10 micrometers; less than 40% by weight of semi-structural minerals; and 0.1 to 13 weight percent of an additive;

heating the polyamide composition;

filling the mold cavity with a heated polyamide composition;

cooling the heated polyamide composition to form the injection molded article.

19. The process of claim 18 further comprising etching the surface of the injection molded article with an etching solution, wherein the etching solution does not contain any hexavalent chromium.

20. The method of any one of claims 18 or 19, further comprising plating the etched surface of the injection molded article with a metal comprising one or more of copper, manganese, tin, nickel, iron, chromium, zinc, gold, platinum, cobalt, phosphorus, aluminum, and alloys thereof.

FIELD

The present disclosure generally relates to polyamide compositions. In particular, the present disclosure relates to (reinforced) polyamide compositions for metallized injection molded articles that exhibit excellent surface appearance, such as smoothness and distinctness of image, as well as excellent mechanical properties.

Background

Polyamide compositions are used in a variety of applications due to their excellent mechanical properties. In particular, polyamide compositions comprising reinforcing fillers significantly improve the strength and stiffness of injection molded articles. For example, the polyamide composition may contain reinforcing fillers, such as glass fibers, to improve mechanical properties or to reduce the cost of the material. The use of high glass loadings in thermoplastics tends to increase the stiffness (flexural), e.g., tensile and flexural modulus, and strength, e.g., tensile and flexural strength, of the reinforced plastic. However, glass fibers have a negative impact on the surface quality and aesthetics of injection molded articles.

Particulate fillers are often added to polyamide compositions to achieve the desired surface appearance of the injection molded article. However, the addition of particulate fillers to glass fiber reinforced polyamide compositions significantly impairs the mechanical properties, in particular the tensile strength, the ultimate elongation and the impact resistance. In the resulting composition, little particulate filler is able to bind the glass fibers and the molded part has reduced tensile strength and impact resistance. On the one hand, the addition of particulate fillers to glass fiber reinforced injection molded articles brings about the desired coloration or functionality, but on the other hand, it leads to deterioration of mechanical properties, such as tensile strength and impact resistance.

Furthermore, if the glass fibers and/or particulate filler are present in large amounts, the surface appearance of the article may become unsatisfactory, for example from an aesthetic point of view. In many applications, the polyamide composition must form an injection molded article having a desired surface quality, such as gloss or reflectance. For example, parts for the automotive industry require injection molded articles with metal-like properties, which are achieved by highly filled reinforced molding compounds. However, after molding, the glass fibers and/or particulate fillers on the outer surface of the article create a dull or matte finish, and these fibers interfere with the adhesion of subsequent coatings or platings that would otherwise cover the fibers. In the case of thin-walled components, a high flow length of the molding compound is necessary, but this is not at all or only poorly achieved when using glass fibers.

Other types of filled or reinforced plastics have similar problems. Conventional "high modulus" materials contain glass or mica or other fillers that can increase the modulus or stiffness of the material. Examples include glass-filled polybutylene terephthalate (PBT), Polyamide (PA), Acrylonitrile Butadiene Styrene (ABS), polycarbonate/acrylonitrile butadiene styrene (PC/ABS), polypropylene (PP), and the like. However, the addition of fillers also has a negative effect on the surface quality of the component. Thus, these types of materials are molded in low gloss texturing applications. These parts can also be painted, but often require a primer to cover surface imperfections before a topcoat layer. Due to the problems associated with fillers, "aesthetic" materials are typically amorphous resins without fillers that are easily color molded, painted, or metallized. These materials include unfilled PBT, PA, ABS, PC/ABS, PP, polyphenylene oxide (PPO), and the like. Unfortunately, these materials do not provide the structural strength necessary for many metal replacement applications.

There is still an increasing need for polyamides which, in addition to an excellent surface appearance and the possibility of more complex designs, can provide better mechanical properties, reduced equipment wear and which are capable of improving productivity, saving costs and realizing alternative designs.

SUMMARY

According to one embodiment, the present disclosure relates to a polyamide composition comprising: 40 to 80 weight percent of a polyamide; 0.5 to 40 weight percent of an etchable filler; 5 to 30 wt% of glass fibers having an average diameter of at most 10 microns; less than 40% by weight semi-structural minerals (semi-structural minerals); and 0.1 to 13% by weight of an additive. In some embodiments, the polyamide comprises PA-6, PA4,6, PA-6,9, PA-6,10, PA-6,12, PA11, PA12, PA9,10, PA9,12, PA9,13, PA9,14, PA9,15, PA-6,16, PA9,36, PA10,10, PA10,12, PA10,13, PA10,14, PA12,10, PA12,12, PA12,13, PA12,14, PA-6,13, PA-6,15, PA-6,16, PA-6,13, PAMXD,6, PA4T, PA5T, PA 6T, PA10T, PA12T, PA4, PA T, PA5T, PA T, terpolymers and mixtures thereof. In some embodiments, the polyamide is a copolymer comprising PA-6,6 and PA-6I, wherein PA-6I is from 2 wt% to 20 wt%. In some embodiments, the polyamide is a terpolymer comprising PA-6, PA-6, and PA-6I, wherein the terpolymer comprises 2 to 20 weight percent PA-6I and 2 to 20 weight percent PA-6. In some embodiments, the additive comprises at least one of: inorganic stabilizers, organic stabilizers, flame retardants, lubricants, dyes, pigments, nucleating agents, metal flakes, impact modifiers, antistatic agents, conductivity additives, mold release agents, optical brighteners, adhesion promoters, aging inhibitors, antioxidants, antiozonants, light stabilizers, ultraviolet absorbers, ultraviolet blockers, inorganic heat stabilizers, organic heat stabilizers, processing aids, crystallization promoters, crystallization retarders, flow aids, fibersA fibrous material and a particulate filler. In some embodiments, the additive comprises 1 to 10 wt% of a pigment, 0.05 to 1 wt% of a lubricant, and/or 0.25 to 2 wt% of a processing aid, wherein the pigment comprises thermally stable nigrosine, wherein the lubricant comprises zinc stearate, and wherein the processing aid comprises a substituted piperidine compound. In some embodiments, the polyamide composition includes 0.5 wt% to 25 wt% etchable filler, and the etchable filler is coated with one or more of an organosilane coating, a vinylsilane coating, or an aminosilane coating. In some embodiments, the etchable filler comprises one or more of magnesium hydroxide, calcium carbonate, and wollastonite. In some embodiments, the glass fibers have an average diameter of 4 to 8 microns. In some embodiments, the composition comprises a semi-structural mineral, wherein the semi-structural mineral comprises one or more of kaolin, mica, talc, and wollastonite. In some embodiments, the composition has an image distinctness of greater than 50 as measured by a Byk Gardner Wave Scan meter, and wherein the composition has an R-value of greater than 5 as measured by a Byk Gardner Wave Scan meter. In some embodiments, the composition has 1.25g/cm³To 1.6g/cm³And wherein the composition has a melting point of 220 ℃ to 260 ℃. In some embodiments, the polyamide is a copolymer comprising PA-6,6 and PA-6I, wherein the composition comprises glass fibers having an average diameter of 4 microns to 8 microns, wherein the composition has 1.3g/cm³To 1.6g/cm³Wherein the composition has an image distinctness of greater than 65 as measured by a Byk Gardner Wave Scan instrument, wherein the composition has an R value of greater than 7 as measured by a Byk Gardner Wave Scan instrument. In some embodiments, the polyamide is a terpolymer comprising PA-6, PA-6I, and PA-6, wherein the composition comprises glass fibers having an average diameter of 4 microns to 8 microns, wherein the composition has 1.3g/cm³To 1.6g/cm³Wherein the composition has a density as measured by Byk Gardner WaveA Scan instrument measuring an image distinctness of greater than 65, wherein the composition has an R-value of greater than 7 as measured by a Byk Gardner Wave Scan instrument. In some embodiments, an injection molded article is formed from the composition described herein, wherein the injection molded article is plated with a metal (plating) comprising one or more of copper, manganese, tin, nickel, iron, chromium, zinc, gold, platinum, cobalt, phosphorus, aluminum, and alloys thereof.

In some embodiments, the present disclosure relates to a polyamide composition comprising: 40 to 80 weight percent of a polyamide; 0.5 to 40 weight percent silane coated magnesium hydroxide; 5 to 30 wt% of glass fibers having an average diameter of at most 10 microns; less than 40% by weight kaolin; and 0.1 to 13% by weight of an additive. In some embodiments, the additive comprises 0.5 to 10 weight percent of thermally stable nigrosine, 0.05 to 1 weight percent of zinc stearate, and/or 0.25 to 2 weight percent of a substituted piperidine compound.

In some embodiments, the present disclosure relates to a method of making an injection molded article comprising: provided is a polyamide composition comprising: 40 to 80 weight percent of a polyamide; 0.5 to 40 weight percent of an etchable filler; 5 to 30 wt% of glass fibers having an average diameter of at most 10 microns; less than 40% by weight of semi-structural minerals; and 0.1 to 13 weight percent of an additive; heating the polyamide composition; filling the mold cavity with a heated polyamide composition; cooling the heated polyamide composition to form the injection molded article. In some embodiments, the method further comprises etching the surface of the injection molded article with an etching solution, wherein the etching solution does not comprise any hexavalent chromium. In some embodiments, the method further comprises plating the etched surface of the injection molded article with a metal comprising one or more of copper, manganese, tin, nickel, iron, chromium, zinc, gold, platinum, cobalt, phosphorus, aluminum, and alloys thereof.

Detailed description of the invention

Introduction to the design reside in

In general, the present disclosure relates to polyamide compositions and injection molded articles made therefrom that can be plated, e.g., metal coated, to form injection molded articles having desirable structural and aesthetic properties. In some embodiments, the polyamide composition comprises 40 to 80 weight percent polyamide, 0.5 to 40 weight percent etchable filler, 5 to 30 weight percent glass fiber, optionally less than 40 weight percent semi-structural mineral, and optionally 0.1 to 13 weight percent additives. The polyamide composition comprises a specific combination of polyamide, glass fibres, etchable filler, semi-structural mineral (optional) and additives (optional), which has been found to give injection moulded articles a synergistic combination of excellent surface appearance and excellent mechanical properties. In addition, the resulting injection molded article can be plated to form an article that is substantially free of visual defects on the surface and has high peel strength. The polyamide composition is advantageously used in structural applications where both the mechanical properties and the surface appearance of the injection molded article are important.

As discussed above, conventional polymer compositions for injection molding applications fail to achieve good surface appearance qualities while maintaining desirable mechanical properties. For example, conventional polymer compositions add high concentrations of glass fibers to improve the mechanical properties of the resulting molded articles, such as peel strength, density, and stiffness. However, polyamide compositions with glass fibers suffer from surface appearance defects. For example, the resulting injection molded product has a poor appearance due to the presence of glass fibers on the surface of the molded article.

In addition, other types of filled or reinforced plastics have similar problems. Conventional "high modulus" materials contain glass or mica or other fillers that can increase the modulus or stiffness of the material. However, the addition of fillers also has a negative effect on the surface quality of the moldings. Thus, these types of materials are molded in low gloss texturing (non-aesthetic) applications. As noted above, the aesthetic material is typically an unfilled amorphous resin that is easily color molded, painted, or metallized. However, these materials do not provide the structural strength necessary for many metal replacement applications.

It has now surprisingly and unexpectedly been found that a polyamide composition having specific amounts of polyamide, glass fibers, surface treated etchable filler, optional minerals and optional additives forms a reinforced injection molded article exhibiting improved aesthetic and mechanical properties. The synergistic combination of the components of the polyamide composition improves the surface appearance of the injection molded article while providing structural integrity to the resulting injection molded article. Furthermore, by employing glass fibers having a specific diameter and/or length, the polyamide composition surprisingly exhibits a good surface appearance at high glass loadings compared to conventional reinforced polyamide compositions. It has been found that a polyamide composition comprising the above components improves the surface appearance of injection molded articles as characterized by orange peel Rating (R-value), distinctness of image (DOI), long and short wavelength.

The polyamide compositions disclosed herein provide structural and aesthetic properties. In some cases, these combinations may be effective in replacing conventional ABS and PC/ABS injection molded articles without structural integrity (purely decorative). In addition, conventional ABS and PC/ABS have low endothermic temperature (HDT) and cannot tolerate high temperature paint layers, making it difficult to apply aesthetic coatings. Advantageously, the polyamide composition has a high HDT and does not form blisters during high temperature coating, which provides an additional manufacturing option.

The specific combination of copolymers, such as PA-6,6/6I and/or terpolymers, such as PA-6,6/6I/6, in the polyamide composition has been shown to enhance the surface appearance of injection molded articles. The use of specific polyamides has been found to increase the melting point of the polyamide (to a relatively high range). Advantageously, the higher melting point of the polyamide prevents etch-induced blistering and also reduces scrap rate compared to conventional polyamide compositions. By employing specific polyamides, such as the copolymers and terpolymers described herein, it is also beneficial to extend the processing time and temperature range for injection molding applications.

The polyamide compositions described herein are also formed into injection molded articles that are capable of being strongly bonded to a coating, such as a chrome coating. In particular, the polyamide composition uses surface treated etchable fillers to make platable injection molded articles with significantly higher peel strength, which contributes to the durability of the molded articles while achieving good surface aesthetics. For example, the polyamide composition includes a surface treated etchable filler that improves the etching properties of the resulting injection molded article. The improved etching properties provide high peel strength at the interface between the surface of the injection molded article and the metal coating.

It has also been found that optionally providing certain additives in specific amounts beneficially improves the surface appearance, structural properties and processability of injection molded articles formed from the polyamide composition. The additives may be, for example, specific pigments, lubricants and/or processing aids. In some aspects, the polyamide composition comprises 1 to 10 weight percent pigment, 0.05 to 1 weight percent lubricant, and/or 0.25 to 2 weight percent processing aid. Synergistic combinations of performance characteristics are discussed in more detail herein.

Polyamide

The polyamide composition may comprise a wide variety of polyamides. In some embodiments, the polyamide may comprise PA-6, PA4,6, PA-6,9, PA-6,10, PA-6,12, PA11, PA12, PA9,10, PA9,12, PA9,13, PA9,14, PA9,15, PA-6,16, PA9,36, PA10,10, PA10,12, PA10,13, PA10,14, PA12,10, PA12,12, PA12,13, PA12,14, PA-6,13, PA-6,15, PA-6,16, PA-6,13, PAMXD,6, PA4T, PA5T, PA-6T, PA9T, PA10T, PA12T, PA4I, PA5I, PA 6I, PA10, PA10I, terpolymers and mixtures thereof.

In some embodiments, the polyamide composition may comprise one or more polyamides, such as copolymers and/or terpolymers. It has been found that the use of a copolymer or terpolymer not only enhances the surface appearance of the injection molded article, but also increases the melting point of the resulting injection molded article. By using a copolymer or terpolymer in the polyamide composition, the resulting injection molded article achieves desirable mechanical properties and surface appearance. For example, in some embodiments, the polyamide composition comprises a copolymer or terpolymer of PA-6, and PA-6I. In some aspects, the polyamide composition includes one or more of PA-6,6/6, PA-6,6/6I, and PA-6, 6/6/I.

In some embodiments, the polyamide composition may comprise a copolymer of PA-6, 6/6I. In some embodiments, the copolymer of PA-6,6/6I comprises PA-6I in an amount of 1 to 20 wt%, e.g., 4 to 19 wt%, 6 to 18 wt%, 10 to 17 wt%, 12 to 16 wt%, or 14 to 16 wt%, based on the total weight of the copolymer. As an upper limit, the copolymer of PA-6,6/6I contains PA-6I in an amount of less than 20 wt%, such as less than 19 wt%, less than 18 wt%, less than 17 wt%, less than 16 wt%, or less than 15 wt%. With respect to the lower limit, the copolymer of PA-6,6/6I contains PA-6I in an amount greater than 1 wt%, e.g., greater than 2 wt%, greater than 4 wt%, greater than 6 wt%, greater than 8 wt%, greater than 10 wt%, or greater than 12 wt%. The balance of the copolymer may comprise PA-6, 6.

In some aspects, the polyamide composition can comprise a PA-6, 6-containing terpolymer. In some embodiments, the terpolymer may comprise PA-6,6 in an amount of 60 wt% to 98 wt%, such as 65 wt% to 96 wt%, 70 wt% to 90 wt%, 75 wt% to 85 wt%, or 80 wt% to 85 wt%, based on the total weight of the terpolymer. As an upper limit, the terpolymer may include PA-6,6 in an amount less than 98 wt%, such as less than 96 wt%, less than 94 wt%, less than 92 wt%, less than 90 wt%, or less than 85 wt%. With respect to the lower limit, the terpolymer may comprise PA-6,6 in an amount greater than 60 wt%, for example greater than 65 wt%, greater than 70 wt%, greater than 75 wt%, greater than 80 wt%, or greater than 84 wt%.

In some embodiments, the polyamide composition may comprise a PA-6I containing terpolymer. In some embodiments, the terpolymer may comprise PA-6I in an amount of 2 wt% to 20 wt%, such as 4 wt% to 18 wt%, 5 wt% to 16 wt%, 6 wt% to 14 wt%, or 8 wt% to 12 wt%, based on the total weight of the terpolymer. As an upper limit, the terpolymer may include PA-6I in an amount less than 20 wt%, such as less than 18 wt%, less than 16 wt%, less than 14 wt%, less than 12 wt%, or less than 10 wt%. With respect to the lower limit, the terpolymer may include PA-6I in an amount greater than 2 wt%, such as greater than 3 wt%, greater than 4 wt%, greater than 5 wt%, greater than 6 wt%, greater than 7 wt%, or greater than 8 wt%.

In some embodiments, the polyamide composition may comprise a PA-6 containing terpolymer. In some embodiments, the terpolymer may comprise PA-6 in an amount of 1 to 15 weight percent, such as 2 to 12 weight percent, 3 to 10 weight percent, 4 to 8 weight percent, or 5 to 7 weight percent, based on the total weight of the terpolymer. As an upper limit, the terpolymer may comprise PA-6 in an amount of less than 15 wt%, such as less than 14 wt%, less than 12 wt%, less than 10 wt%, less than 8 wt%, or less than 7 wt%. With respect to the lower limit, the terpolymer may comprise PA-6 in an amount greater than 1 wt%, such as greater than 2 wt%, greater than 3 wt%, greater than 4 wt%, greater than 5 wt%, or greater than 6 wt%.

In some embodiments, the polyamide composition may comprise a terpolymer of PA-6, 6/6I/6. In some aspects, the terpolymer of PA-6,6/6I/6 comprises 60 to 98 weight percent PA-6, 2 to 20 weight percent PA-6I, and 1 to 15 weight percent PA-6. In some aspects, the terpolymer of PA-6,6/6I/6 includes 1 to 20 wt% PA-6, e.g., 2 to 18 wt%, 4 to 16 wt%, 5 to 12 wt%, or 6 to 10 wt%. In some aspects, the PA-6,6/6I/6 terpolymer includes less than 14 wt% PA-6, less than 12 wt%, less than 10 wt%, less than 8 wt%, or less than 7 wt%. In some aspects, the PA-6,6/6I/6 terpolymer includes greater than 1 wt% PA-6, such as greater than 2 wt%, greater than 3 wt%, greater than 4 wt%, greater than 5 wt%, or greater than 6 wt%.

In some aspects, the polyamide composition may comprise a polyamide made by ring opening polymerization or polycondensation, including copolymerization and/or copolycondensation, of a lactam. Without being bound by theory, these polyamides may include, for example, those made from propiolactam, butyrolactam, valerolactam, and caprolactam. For example, in some embodiments, the polyamide is a polymer derived from the polymerization of caprolactam. In addition, the polyamide composition may comprise a polyamide made by copolymerization of a lactam and a nylon, such as the copolymerization product of caprolactam and PA-6, 6.

In some embodiments, the polyamide may be a condensation product of one or more dicarboxylic acids, one or more diamines, one or more aminocarboxylic acids, and/or a ring-opening polymerization product of one or more cyclic lactams, such as caprolactam and laurolactam. In some aspects, the polyamide may comprise aliphatic, aromatic, and/or semi-aromatic polyamides and may be a homopolymer, copolymer, terpolymer, or higher order polymer. In some aspects, the polyamide comprises a blend of two or more polyamides. In some embodiments, the polyamide comprises an aliphatic or aromatic polyamide or a blend of two or more polyamides.

In some aspects, the dicarboxylic acid may comprise one or more of adipic acid, azelaic acid, terephthalic acid, isophthalic acid, sebacic acid, and dodecanedioic acid. In some aspects, the dicarboxylic acid can comprise adipic acid, isophthalic acid, and terephthalic acid. In some aspects, the dicarboxylic acid may comprise an aminocarboxylic acid, such as 11-aminododecanoic acid.

In some aspects, the diamine can comprise one or more of butanediamine, hexanediamine, octanediamine, nonanediamine, 2-methylpentanediamine, 2-methyloctanediamine, trimethylhexanediamine, bis (p-aminocyclohexyl) methane, m-xylylenediamine, p-xylylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, butanediamine, pentanediamine, hexanediamine, and the like. Other examples of only exemplary aromatic diamine components include phenylenediamines, such as 1, 4-diaminobenzene, 1, 3-diaminobenzene, and 1, 2-diaminobenzene; diphenyl (thio) ether diamines such as 4,4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl ether and 4,4 ' -diaminodiphenyl sulfide; benzophenone diamines such as 3,3 '-diaminobenzophenone and 4, 4' -diaminobenzophenone; diphenylphosphindiamines such as 3,3 '-diaminodiphenylphosphine and 4, 4' -diaminodiphenylphosphine; diphenylalkylenediamines such as 3,3 '-diaminodiphenylmethane, 4' -diaminodiphenylmethane, 3 '-diaminodiphenylpropane and 4, 4' -diaminodiphenylpropane; diphenylsulfide diamines such as 3,3 '-diaminodiphenylsulfide and 4, 4' -diaminodiphenylsulfide; diphenylsulfone diamines such as 3,3 '-diaminodiphenylsulfone and 4, 4' -diaminodiphenylsulfone; and benzidines such as benzidine and 3, 3' -dimethylbenzidine.

In some embodiments, the polyamide may comprise a semi-aromatic polyamide. In some aspects, the semi-aromatic polyamide may comprise polymetaphenylene diamide, polyterephthalamide, or PA-MXD, 6. In some aspects, the polyterephthalamide comprises PA-12, T, PA-10, T, PA-9, T, PA-6, T/6, PA-6, T/D, T, copolymers, terpolymers, or mixtures thereof. In some aspects, the semi-aromatic polyamide may comprise hexamethylene isophthalamide (PA-6T/6I), hexamethylene adipamide (PA-61/6,6), hexamethylene adipamide/hexamethylene terephthalamide/hexamethylene isophthalamide copolyamide (PA-6,6/6, T/6, I); poly (caprolactam-hexamethylene terephthalamide) (PA-6/6, T); and copolymers, terpolymers and blends of these polymers.

In some embodiments, the polyamide may comprise an aliphatic polyamide. In some embodiments, the polyamide comprises aliphatic polyamide copolymers and terpolymers, comprising PA-6, 6/6; PA-6, 6/68; PA-6, 6/610; PA-6, 6/612; PA-6, 6/10; PA-6, 6/12; PA-6/68; PA-6/610; PA-6/612; PA-6/10; PA-6/12; PA-6/6, 6/610; PA-6/6, 6/69; PA-6/6, 6/11; PA-6/6, 6/12; PA-6/610/11; PA-6/610/12; and PA-6/6,6/PACM (bis-p- { aminocyclohexyl } methane).

In some aspects, the polyamide comprises a physical blend of aliphatic, semi-aromatic, and/or aromatic polyamides to obtain properties that are intermediate or synergistic in the properties of the respective polyamides.

Etchable filler

The polyamide composition may further comprise an etchable filler, such as an etchable particulate filler. In some embodiments, etchable fillers can be partially removed and/or altered (to achieve etching) by treatment (acid, base, heat, solvent, etc.) under conditions that do not adversely affect the polymer composition. In some embodiments, the etchable filler is a material that is removable by an acidic aqueous solution, for example, an etching material such as magnesium hydroxide, calcium carbonate, or zinc oxide. Since the polymer matrix is generally substantially unaffected by the treatment, only the etchable filler near the surface of the injection molded article is affected, e.g., completely or partially removed.

The etchable filler can be etched or removed by a metallized surface preparation process, thereby establishing a surface roughness that can improve the adhesion of the resulting injection molded article to the metal coating. The etchable filler (e.g., acid etchable) can be any filler that can be removed by the surface preparation process. The filler may be used alone or in combination with other fillers. In some embodiments, the etchable filler is magnesium hydroxide or calcium carbonate. It has been found that the surface treated magnesium hydroxide provides higher peel strength to the resulting injection molded article.

In some aspects, the etchable filler can be etched with an etching solution. Like the treatment temperature, agitation and time, the pH of the etching solution used to treat the surface of the polymeric article is an important aspect of the treatment. In some aspects, the etching solution can be an aqueous acidic liquid mixture having a pH of less than 7, e.g., less than 6, less than 5, less than 4, less than 3, or less than 2. In some embodiments, the etching solution may be an aqueous acidic liquid mixture having a pH of 1-7, e.g., 2-6, 3-6, 4-6, 5-6, or 2-5. Acids such as inorganic and organic acids can be used to establish acidity. Non-limiting examples of inorganic acids that can be used as etchants include hydrochloric acid, sulfuric acid, nitric acid, and hydrofluoric acid. Non-limiting examples of organic acids include oxalic acid, acetic acid, benzoic acid, and the like. Buffering systems (buffers) may also be established by the presence of one or more of bicarbonate, fluorohydride, bisulfate, or similar compounds along with one or more of carbonic acid, carbonate, hydrofluoric acid, fluoride, sulfuric acid, sulfate, or similar compounds.

In some embodiments, the polyamide composition comprises the etchable filler in an amount of 0.5 to 40 wt%, such as 1 to 38 wt%, 2 to 36 wt%, 4 to 32 wt%, 6 to 28 wt%, 8 to 24 wt%, 10 to 20 wt%, 12 to 18 wt%, or 14 to 16 wt%, based on the total weight of the polyamide composition. With respect to the upper limit, the polyamide composition includes less than 40 wt% etchable filler, e.g., less than 38 wt%, less than 34 wt%, less than 30 wt%, less than 26 wt%, less than 22 wt%, less than 18 wt%, or less than 16 wt%. With respect to the lower limit, the polyamide composition includes greater than 0.5 wt.% etchable filler, e.g., greater than 1 wt.%, greater than 2 wt.%, greater than 4 wt.%, greater than 6 wt.%, greater than 8 wt.%, greater than 10 wt.%, greater than 12 wt.%, greater than 14 wt.%, or greater than 15 wt.%.

Conventionally, polyamide compositions for injection molded articles use at least 25 weight percent etchable filler in the polyamide composition to achieve the desired plating properties. It has been found that the use of less than 25 weight percent etchable filler in a polyamide composition provides improved release properties, such as peel strength, for metal plating applications. In other words, the present polyamide compositions are capable of achieving the desired plating properties at lower loadings of etchable filler. In some aspects, the polyamide composition includes less than 25 wt% etchable filler, e.g., less than 24 wt%, less than 22 wt%, less than 20 wt%, less than 18 wt%, or less than 16 wt%. In some aspects, the polyamide composition comprises about 15 wt% etchable filler.

In some embodiments, the etchable filler has an average particle size of 0.1 to 2.0 microns, e.g., 0.2 to 1.9 microns, 0.3 to 1.8 microns, 0.4 to 1.6 microns, 0.5 to 1.4 microns, 0.6 to 1.2 microns, or 0.8 to 1.1 microns. With respect to the upper limit, the etchable filler has an average particle size of less than 2.0 microns, e.g., less than 1.8 microns, less than 1.7 microns, less than 1.6 microns, less than 1.5 microns, less than 1.4 microns, less than 1.2 microns, or less than 1 micron. With respect to the upper limit, the etchable filler has an average particle size greater than 0.1 microns, e.g., greater than 0.2 microns, greater than 0.3 microns, greater than 0.4 microns, greater than 0.5 microns, greater than 0.6 microns, greater than 0.7 microns, or greater than 0.8 microns.

In some embodiments, the etchable filler has a d of 1.4 to 1.9 microns, e.g., 1.5 to 1.8 microns or 1.6 to 1.7 microns₉₀. In some embodiments, the etchable filler has a d of 0.8 to 1.1 microns, e.g., 0.85 to 1.05 microns or 0.9 to 1 micron₅₀. In some embodiments, the etchable filler has a d of 0.3 to 0.6 microns, e.g., 0.35 to 0.55 microns or 0.4 to 0.5 microns₁₀. In this respect, d₂₀、d₅₀And d₉₀Based on the volume distribution (d) as measured by laser diffraction, e.g. using a laser diffraction software package₅₀Is the median particle size value).

In some embodiments, the average particle size of the etchable filler can have a generally monomodal distribution. For example, all particles may have the same average particle size, or as another example, the particles may have a distribution of average particle sizes, such as a gaussian distribution, such that the average particle size fluctuates above and below a certain mean.

In some embodiments, the average particle size of the etchable filler can have a multimodal distribution. For example, the average particle size may have a bimodal distribution or a higher modal distribution, such as trimodal. The multimodal distribution of particle sizes facilitates, for example, the adjustment of the properties of the polyamide composition. In addition to size distribution, other particle characteristics, such as particle shape and particle composition, may surround a single mean distribution or may have a multimodal distribution. These other distributions of particle characteristics may also be used to adjust one or more properties of the injection molded article.

In some aspects, the particle size distribution of the etchable filler can have a first maximum of 1.4 to 1.9 microns and a second maximum of 2.4 to 4.4 microns. In some aspects, the particle size distribution can have a first maximum of 0.8 microns to 1.1 microns and a second maximum of 1.5 microns to 2 microns. In some aspects, the particle size distribution can have a first maximum of 0.3 microns to 0.6 and a second maximum of 0.7 microns to 1.1 microns. In some aspects, the bimodal distribution of particle sizes can be any one of a combination of these ranges.

In some embodiments, the etchable filler has 6m²G to 12m²G, e.g. 7m²G to 11.5m²/g、8m²G to 11m²(ii)/g, or 9m²G to 10m²Surface area in g. In terms of an upper limit, the etchable filler has less than 12m²G, e.g. less than 11.5m²(ii) g is less than 11m²A ratio of the water to the water of less than 10.5m²A/g or less than 10m²Surface area in g. With respect to the lower limit, the etchable filler has greater than 6m²In g, e.g. greater than 6.5m²A ratio of the total of the carbon atoms to the carbon atoms of greater than 7m²A ratio of the water to the water of more than 7.5m²A/g or more than 8m²Surface area in g.

In some embodiments, the etchable filler comprises a metal salt and a mineral, such as: (a) a metal carbonate, wherein the metal comprises one or more of barium, bismuth, cadmium, calcium, cobalt, copper, lead, magnesium, iron, nickel, and zinc; (b) a metal oxide, wherein the metal comprises one or more of aluminum, antimony, bismuth, cadmium, cerium, cobalt, copper, gallium, germanium, indium, iron, lead, manganese, nickel, tin, zinc, and zirconium; (c) a metal hydroxide, wherein the metal comprises one or more of bismuth, cerium, cobalt, copper, magnesium, and manganese; (d) a metal oxalate in which the metal comprises one or more of aluminum, calcium, cobalt, iron, lead, magnesium, manganese, nickel, and tin; (e) a metal orthophosphate in which the metal comprises one or more of aluminum, cadmium, cerium, chromium, cobalt, lead, lithium, magnesium, nickel, strontium, tin and zinc; (f) a metal metasilicate, wherein the metal comprises one or more of barium, calcium (wollastonite), lead, and lithium; and (g) a metal pyrophosphate, wherein the metal comprises one or more of magnesium, manganese, and nickel.

In addition, these etchable fillers can be treated with compounds to alter the properties of the etchable filler. Advantageously, treated, e.g., surface treated, etchable fillers used in polyamide compositions can make the compositions more compatible with polyamides, e.g., nylon. In other aspects, the treated etchable filler can also provide a compatible surface for etching. For example, the etchable filler may be coated with a coupling agent. In some embodiments, treated etchable fillers may be provided in the polyamide composition. In some embodiments, the etchable filler may be extruded with a coupling agent to form a treated etchable filler.

In some aspects, the etchable filler is coated with a silane coupling agent. The silane coupling agent may comprise vinylsilanes, such as vinyltris (β -methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acryloxysilane, such as γ -methacryloxypropyltrimethoxysilane, epoxysilanes, such as β - (3, 4-epoxy-cyclohexyl) ethyltrimethoxysilane, β - (3, 4-epoxy-cyclohexyl) methyltrimethoxysilane, β - (3, 4-epoxy-cyclohexyl) ethyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane and γ -glycidoxypropyltriethoxysilane, aminosilanes, such as N- β - (aminoethyl) - γ -aminopropyltriethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, N-t-methacryloxypropyltrimethoxysilane, N-c-ethyltrimethoxysilane, N-t-butyltrimethoxysilane, N-butyltrimethoxysilane, N-, N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane and N-phenyl-gamma-aminopropyltriethoxysilane, and thiosilanes such as gamma-mercaptopropyltrimethoxysilane and gamma-mercaptopropyltriethoxysilane. In some aspects, the etchable filler is coated with a vinyl silane coupling agent. In some aspects, the etchable filler is surface treated with an aminosilane coupling agent.

It has been found that the use of etchable fillers comprising magnesium hydroxide coated with a silane coupling agent improves the thermal properties and peel strength of injection molded articles formed from polyamide compositions. In some embodiments, the silane coupling agent comprises one or more of fatty acids, alkyl silanes, organotitanates, organozirconates, aminosilanes, vinyl silanes, or siloxane derivatives. In some aspects, the vinyl silane coating on the etchable filler provides a polymer composition with high peel strength.

In some embodiments, the etchable filler, e.g., magnesium hydroxide, includes 0.05 wt% to 5.0 wt%, e.g., 0.08 wt% to 4.5 wt%, 0.1 wt% to 4.0 wt%, 0.5 wt% to 3.5 wt%, 1 wt% to 3 wt%, or 1.5 wt% to 2.5 wt% of the silane coupling agent, based on the total weight of the etchable filler. With respect to the upper limit, the etchable filler includes less than 5.0 wt% silane coupling agent, e.g., less than 4.0 wt%, less than 3.5 wt%, or less than 3.0 wt%, or less than 2.0 wt%. With respect to the lower limit, the etchable filler includes greater than 0.05 wt% silane coupling agent, e.g., greater than 0.08 wt%, greater than 0.1 wt%, greater than 0.5 wt%, or greater than 1 wt%.

In some embodiments, the etchable filler can be treated with other compounds to alter the properties of the polyamide composition. In some aspects, the etchable filler is treated with a coupling agent, such as an isocyanate compound, an organosilane compound, an organotitanate compound, an organoborane compound, or an epoxy compound; a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound or an organophosphorus compound; crystal nucleating agents, such as talc, kaolin, organic phosphorus compounds or polyetheretherketone; metal soaps such as montan wax, lithium stearate, or aluminum stearate; mold release agents, such as ethylenediamine/stearic acid/sebacic acid polycondensates or organosilicon compounds; color protection agents, such as hypophosphite salts; and other common additives such as lubricants, ultraviolet protection agents, colorants, flame retardants, and blowing agent treatments.

Semi-structural mineral

The polyamide composition may optionally include one or more semi-structural minerals, such as a semi-structural mineral filler. The polyamide composition may include any semi-structural mineral having various average diameters, cross-sections, lengths, and aspect ratios. In some aspects, the semi-structural mineral may include constituents such as glass, carbon, graphite, polymers, and the like. In some embodiments, the semi-structural mineral comprises kaolin particles. The optional semi-structural mineral used in the polyamide composition may be present in an amount of less than 40 weight percent based on the total weight of the polyamide composition.

In some embodiments, the polyamide composition may include the semi-structural mineral in an amount of 0.01 to 40 weight percent, such as 1 to 36 weight percent, 2 to 32 weight percent, 6 to 28 weight percent, 8 to 24 weight percent, 10 to 20 weight percent, 12 to 18 weight percent, or 14 to 16 weight percent. As an upper limit, the polyamide composition comprises less than 40 wt% of the semi-structural mineral, such as less than 36 wt%, less than 32 wt%, less than 28 wt%, less than 24 wt%, less than 20 wt%, or less than 16 wt%. With respect to the lower limit, the polyamide composition comprises more than 0 wt% of the semi-structural mineral, for example more than 2 wt%, more than 4 wt%, more than 8 wt%, more than 10 wt%, more than 12 wt% or more than 14 wt%. In some embodiments, the polyamide composition may be substantially free of semi-structural minerals, e.g., free of semi-structural minerals.

In some aspects, the semi-structural mineral may comprise one or more of: talc, mica, silicates, quartz, wollastonite, kaolin, calcined kaolin, hydrous kaolin, silicic acid, magnesium carbonate, chalk, ground or cut calcium carbonate, lime, feldspar, inorganic pigments such as barium sulfate, zinc oxide, zinc sulfide, titanium dioxide, iron sesquioxide, manganese iron oxide, metal oxides, especially spinels, such as copper-iron spinel, copper-chromium oxide, zinc-iron oxide, cobalt-chromium oxide, cobalt-aluminum oxide, magnesium-aluminum oxide, copper-chromium-manganese composite oxide, copper-manganese-iron composite oxide, rutile pigments such as titanium-zinc-rutile, nickel-antimony-titanate, permanent or magnetizable metals or alloys, concave (concave) silicate fillers, alumina, boron nitride, boron carbide, aluminum nitride, calcium fluoride, and compounds thereof. In some aspects, the semi-structural mineral may be one or more of kaolin, mica, talc, and wollastonite. In some aspects, the semi-structural mineral may be surface treated as described herein.

In some aspects, the semi-structural mineral used in the polyamide composition may be hydrated, such as hydrous kaolin or hydrous clay, to release steam during compounding and moldingThe gas serves to form pores within the polyamide. In some aspects, the composite material may release water chemically bound to the semi-structural mineral when subjected to excessive heat and may also act as a flame retardant. In some aspects, the polyamide composition comprises calcite kaolin, treated kaolin, or mixtures thereof. In some aspects, the kaolin is a surface treated kaolin, such as the commercially available Polarite 102A from Imerys, which is calcined and silane treated kaolin. In some aspects, the semi-structural mineral comprises a calcined and surface treated aluminosilicate, such as Al₂Si₂O₅(OH)₄。

In some embodiments, the polyamide composition may include one or more commercially available semi-structural minerals, such as commercially available kaolin clay. Commercially available semi-structural minerals may include those from Imerys KaolinSB 100s, Polarite 102A, Polarite 502A, Polarite 702A or Polarite 902A from Imerys Kaolin, and/or from BASF445 or555. In some aspects, the commercially available semi-structural mineral may be spray dried and/or powdered, such as spray dried Polarite 702A. In some aspects, a commercially available semi-structural mineral may be mixed with any of the above semi-structural minerals.

Glass fiber

The polyamide composition includes glass fibers, for example, to form a glass reinforced polyamide composition. Glass reinforced polyamide compositions greatly improve the strength, stiffness, heat resistance and impact strength of injection molded articles. In some embodiments, the polyamide composition includes glass fibers in an amount from 10 wt% to 30 wt%, such as from 12 wt% to 28 wt%, from 12 wt% to 26 wt%, from 14 wt% to 24 wt%, from 16 wt% to 22 wt%, or from 18 wt% to 20 wt%. With respect to the upper limit, the polyamide composition comprises less than 30 wt% of glass fibers, such as less than 26 wt%, less than 24 wt%, less than 22 wt%, less than 20 wt%, less than 18 wt%, or less than 16 wt%. With respect to the lower limit, the polyamide composition comprises more than 2 wt.% of glass fibers, for example more than 4 wt.%, more than 8 wt.%, more than 10 wt.%, more than 12 wt.% or more than 14 wt.%.

In some embodiments, the polyamide composition may comprise glass fibers having an average diameter of 1 micron to 10 microns, such as 2 microns to 9.5 microns, 3 microns to 9 microns, 3.5 microns to 8.5 microns, 4 microns to 8 microns, 4.5 microns to 7.5 microns, 5 microns to 7 microns, or 5.5 microns to 6.5 microns. In terms of an upper limit, the polyamide composition comprises glass fibers having an average diameter of at most 10 microns (including 10 microns), such as at most 9.5 microns, at most 9 microns, at most 8.5 microns, at most 8 microns, at most 7.5 microns, or at most 7 microns. With respect to the lower limit, the polyamide composition comprises glass fibers having an average diameter of greater than 1 micron, such as greater than 2 microns, greater than 3 microns, greater than 4 microns, greater than 5 microns, or greater than 6 microns. In some aspects, at least 70% of the glass fibers have a diameter of 1 micron to 10 microns, e.g., at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99%.

In some embodiments, the polyamide composition comprises short glass fibers having a pre-compounding length of 3mm to 5mm and an average diameter of 1 micron to 10 microns. After compounding, the glass fibers may have a length of 0.1mm to 1 mm. In some aspects, the short glass fibers have a circular and/or non-circular cross-section.

In some aspects, the glass fibers comprise a mixture of one or more glass fibers. Glass fibers can be cut to length or "continuous" and have various average diameters, cross-sections, lengths, and aspect ratios. In some aspects, the glass fibers may comprise constituents such as glass, carbon, graphite, graphene, and polymers. In some aspects, the glass fibers are chopped glass fibers having a circular cross-section. In some aspects, mixtures of glass fibers having circular and non-circular cross-sections may also be used to reinforce injection molded articles. In some aspects, the glass fibers, regardless of the shape of the cross-section and the length of the fibers, may comprise one or more of a glass fibers, C glass fibers, D glass fibers, M glass fibers, S glass fibers, and/or R glass fibers and E glass fibers. Possible suitable commercially available glass fibers include NEG T-289 DE-circular cross-section glass fibers from Nippon Electric (E-glass fibers having a diameter of 6.5 microns).

Additive agent

In some embodiments, the polymer composition may optionally include one or more additives. In some embodiments, the additive comprises one or more of catalysts, non-polyamide polymers, adhesion promoters, ions, compounds, preservatives (preservatives) such as heat stabilizers and antioxidants, lubricants, flow enhancers, or other ingredients as known in the art. The additive may include at least one of: inorganic stabilizers, organic stabilizers, flame retardants, lubricants, dyes, pigments, nucleating agents, metal flakes, impact modifiers, antistatic agents, conductivity additives, mold release agents, optical brighteners, adhesion promoters, aging inhibitors, antioxidants, antiozonants, light stabilizers, ultraviolet absorbers, ultraviolet blockers, inorganic heat stabilizers, organic heat stabilizers, processing aids, crystallization promoters, crystallization retarders, flow aids, fibrous materials, and particulate fillers.

In some embodiments, the polyamide composition may include one or more optional additives in an amount of 0.1 to 13 weight percent, e.g., 0.5 to 12 weight percent, 0.8 to 10 weight percent, 1 to 9 weight percent, 2 to 8 weight percent, 3 to 7 weight percent, or 4 to 6 weight percent, based on the total weight of the polyamide composition. With respect to the upper limit, the polyamide composition comprises less than 13 wt% of additives, such as less than 12 wt%, less than 11 wt%, less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 6 wt%, less than 4 wt% or less than 2 wt%. With respect to the lower limit, the polyamide composition comprises more than 0.1 wt% of additives, such as more than 0.1 wt%, more than 0.2 wt%, more than 0.4 wt%, more than 0.6 wt%, more than 0.8 wt%, more than 1 wt% or more than 1.5 wt%.

In some embodiments, the additive comprises at least a pigment. In some aspects, the pigment can be nigrosine. In some embodiments, the polyamide composition comprises the pigment in an amount of 1 to 10 weight percent, such as 2 to 9 weight percent, 3 to 8 weight percent, 4 to 7 weight percent, or 5 to 6 weight percent, based on the total weight of the polyamide composition. With respect to the upper limit, the polyamide composition comprises less than 10 wt% of pigment, such as less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, or less than 5 wt%. With respect to the lower limit, the polyamide composition comprises more than 1% by weight of pigment, for example more than 1.5%, more than 2%, more than 2.5%, more than 3%, more than 4% or more than 4.5% by weight.

In some embodiments, the additive comprises at least a lubricant. In some aspects, the lubricant may be zinc stearate. In some embodiments, the polyamide composition includes the lubricant in an amount of 0.05 wt% to 1 wt%, such as 0.06 wt% to 0.8 wt%, 0.08 wt% to 0.6 wt%, 0.1 wt% to 0.4 wt%, or 0.2 wt% to 0.3 wt%, based on the total weight of the polyamide composition. With respect to the upper limit, the polyamide composition comprises less than 1 wt.% of lubricant, such as less than 0.8 wt.%, less than 0.6 wt.%, less than 0.4 wt.%, less than 0.3 wt.%, less than 0.2 wt.%, or less than 0.15 wt.%. With respect to the lower limit, the polyamide composition comprises more than 0.05 wt.% of the lubricant, for example more than 0.06 wt.%, more than 0.07 wt.%, more than 0.08 wt.%, more than 0.09 wt.%, more than 0.1 wt.%, or more than 0.125 wt.%.

In some embodiments, the additive comprises at least one processing aid. In some embodiments, the polyamide composition includes the processing aid in an amount of 0.25 wt% to 2 wt%, such as 0.3 wt% to 1.8 wt%, 0.4 wt% to 1.6 wt%, 0.8 wt% to 1.4 wt%, or 1.0 wt% to 1.2 wt%, based on the total weight of the polyamide composition. With respect to the upper limit, the polyamide composition includes less than 2 wt% of processing aid, such as less than 1.8 wt%, less than 1.6 wt%, less than 1.4 wt%, less than 1.2 wt%, less than 1.1 wt%, or less than 1 wt%. With respect to the lower limit, the polyamide composition comprises more than 0.25 wt% of processing aid, for example more than 0.3 wt%, more than 0.4 wt%, more than 0.6 wt%, more than 0.7 wt% or more than 0.8 wt%. In some aspects, the processing aid can comprise NYLOSAB S-EED. NYLOSTATB S-EED provides for melt processing of the compound and stability of melt pressure during polymerization. The NYLOSABB S-EED also improves the surface appearance of the injection molded part, including but not limited to, reduction of haze (blush) in narrow part areas or sharp corner areas, such as in gate areas of molded parts.

In some embodiments, the additive in the polyamide composition comprises 1 to 10 weight percent pigment, 0.05 to 1 weight percent lubricant, and/or 0.25 to 2 weight percent processing aid. In some aspects, the pigment comprises a thermally stable nigrosine. In some aspects, the lubricant comprises zinc stearate. In some aspects, the processing aid comprises a substituted piperidine compound, such as NYLOSAB

In some embodiments, the additive may further comprise a crosslinking agent, such as triaminononane. In some aspects, the crosslinking agent is a comonomer used to prepare the copolymer, such as TAN, triaminononane (PA-6,6/6, I/TAN (84.5%/15%/0.5%), using 2.7 to 3.1 microequivalents per gram of acetic acid capping agent). In some aspects, the crosslinking agent is added during polymerization of the polyamide composition.

Properties of Polyamide composition

As mentioned above, the polyamide composition described herein beneficially imparts aesthetic and structural properties to the resulting injection molded article. The specific combination of components in the polyamide composition synergistically improves structural properties of the resulting injection molded article, such as melting point, density, tensile strength, tensile modulus, flexural strength, flexural modulus, elongation and/or HDT, while also improving surface finish, such as DOI and R-values. Unlike ABS or PC/ABS, the physical properties of polyamide compositions have been found to be sufficient for structural engineering applications because their tensile strength and HDT exceed the requirements for engineering plastics.

In some embodiments, the polyamide composition may have a melting point greater than 200 ℃, such as greater than 210 ℃, greater than 220 ℃, greater than 230 ℃, or greater than 240 ℃. In some embodiments, the polyamide can have a melting point of less than 300 ℃, e.g., less than 290 ℃, less than 280 ℃, less than 275 ℃, less than 270 ℃, or less than 260 ℃. In some embodiments, the polyamide can have a melting point of 200 ℃ to 290 ℃, e.g., 210 ℃ to 280 ℃, 220 ℃ to 270 ℃, 230 ℃ to 260 ℃, 235 ℃ to 255 ℃, or 240 ℃ to 250 ℃.

In some embodiments, the polyamide composition may have a density of 1.1g/cm³To 2.0g/cm³E.g. 1.2g/cm³To 1.9g/cm³、1.25g/cm³To 1.85g/cm³、1.3g/cm³To 1.8g/cm³、1.4g/cm³To 1.7g/cm³、1.3g/cm³To 1.6g/cm³Or 1.5g/cm³To 1.7g/cm³The density of (c). In some embodiments, the polyamide composition may have less than 2.0g/cm³E.g. less than 1.9g/cm³Less than 1.8g/cm³Less than 1.7g/cm³Less than 2.5g/cm³Less than 1.6g/cm³Or less than 1.55g/cm³The density of (c). In some embodiments, the polyamide composition may have greater than 1.1g/cm³E.g. greater than 1.2g/cm³More than 1.25g/cm³Greater than 1.3g/cm³More than 1.35g/cm³Greater than 1.4g/cm³Or more than 1.45g/cm³The density of (c).

In some embodiments, the polyamide composition may have a Heat Distortion Temperature (HDT) of 195 ℃ to 225 ℃, e.g., 198 ℃ to 222 ℃, 200 ℃ to 220 ℃, 204 ℃ to 216 ℃, 205 ℃ to 215 ℃, or 210 ℃ to 220 ℃. In some embodiments, the polyamide composition may have an HDT of greater than 195 ℃, e.g., greater than 198 ℃, greater than 200 ℃, greater than 202 ℃, greater than 205 ℃, or greater than 208 ℃. In some embodiments, the polyamide can have an HDT of less than 225 ℃, e.g., less than 222 ℃, less than 220 ℃, less than 218 ℃, less than 215 ℃, or less than 210 ℃.

In some embodiments, the polyamide composition can have a tensile strength of 120MPa to 150MPa, such as 125MPa to 145MPa, 130MPa to 140MPa, 135MPa to 145MPa, or 140MPa to 150 MPa. In some embodiments, the polyamide composition may have a tensile strength of less than 150MPa, such as less than 148MPa, less than 146MPa, less than 144MPa, less than 142MPa, or less than 140 MPa. In some embodiments, the polyamide composition may have a tensile strength greater than 120MPa, such as greater than 122MPa, greater than 124MPa, greater than 126MPa, greater than 128MPa, or greater than 130 MPa. Tensile strength can be measured using ASTM D638 (this year).

In some embodiments, the polyamide composition can have a tensile modulus of 6900MPa to 10,000MPa, such as 7000MPa to 9600MPa, 7200MPa to 9400MPa, 7500MPa to 9000MPa, 7800MPa to 8800MPa, 8000MPa to 8600MPa, or 8200MPa to 8500 MPa. In some aspects, the polyamide composition can have a tensile modulus of less than 10,000MPa, e.g., less than 9800MPa, less than 9400MPa, less than 9200MPa, less than 9000MPa, or less than 8500 MPa. In some aspects, the polyamide composition can have a tensile modulus greater than 6900MPa, such as greater than 7200MPa, greater than 7400MPa, greater than 7800MPa, greater than 8000MPa, or greater than 8200 MPa. Tensile modulus can be measured using ASTM D638 (this year).

In some embodiments, the polyamide composition can have a flexural strength of 160MPa to 220MPa, such as 170MPa to 210MPa, 175MPa to 205MPa, 180MPa to 200MPa, or 185MPa to 195 MPa. In some aspects, the polyamide composition can have a flexural strength of less than 220MPa, such as less than 215MPa, less than 210MPa, less than 205MPa, less than 200MPa, or less than 195 MPa. In some aspects, the polyamide composition can have a flexural strength greater than 160MPa, such as greater than 165MPa, greater than 170MPa, greater than 175MPa, greater than 180MPa, or greater than 185 MPa. Flexural or flexural strength can be measured using ASTM D790 (year).

In some embodiments, the polyamide composition may have an elongation of 1% to 5%, such as 1.5% to 4.5%, 2% to 4%, 2.5% to 3.5%, or 2% to 3%. In some aspects, the polyamide composition can have an elongation of less than 5%, e.g., less than 4.5%, less than 4.0%, less than 3.5%, less than 3.25%, or less than 3%. In some aspects, the polyamide composition can have an elongation of greater than 1%, e.g., greater than 1.5%, greater than 2%, greater than 2.25%, greater than 2.5%, or greater than 2.75%. Elongation can be measured using ASTM D638 (this year).

In some embodiments, the polyamide composition may have 2kJ/m²To 5kJ/m²For example 2.5kJ/m²To 4.5kJ/m²、3kJ/m²To 4kJ/m²、3.5kJ/m²To 4.5kJ/m²Or 4kJ/m²To 5kJ/m²The notched izod impact strength. In some embodiments, the polyamide composition may have less than 5kJ/m²E.g. less than 4.8kJ/m²Less than 4.5kJ/m²Less than 4kJ/m²Less than 3.75kJ/m²Or less than 3.5kJ/m²The notched izod impact strength. In some embodiments, the polyamide composition may have greater than 2g/cm³E.g. greater than 2.2kJ/m²More than 2.4kJ/m²More than 2.6kJ/m²More than 2.8kJ/m²More than 3kJ/m²Or more than 3.2kJ/m²The notched izod impact strength. The impact strength can be measured using ASTM D256 (this year).

It has been found that a polyamide composition comprising a specific combination of polyamide, etchable filler, glass fibers and optional additives improves the surface appearance. The surface appearance of the metallized injection molded article is characterized by nominal orange peel (R-value) and distinctness of image (DOI). The metallized injection molded articles were evaluated using a Byk Gardner Wave Scan Meter (BYK-Gardner, Columbia, Md.) to determine DOI and R values. The R value and DOI can be measured using publicly available experimental parameters and procedures (this year) established by BYK-Gardner.

DOI is an objective appearance criterion for brightness and gloss that includes visual effects from a rough or bumpy coating surface, sometimes referred to as "orange peel". The metallized surface of injection molded articles made from the polyamide compositions described herein exhibit high DOI.

By and with(USA) company orange peel board visual ratings correlated long and short wave calculated R values. Calculating the R value according to formula (I):

R＝10.5-4*log(a-0.02*|b-20|)(I),

longwave is the amplitude variance of the longwave signal, making a major contribution to R (a). Short waves are the amplitude variance of the short wave signal, making a very slight contribution to R (b).

In some embodiments, injection molded articles made from the polyamide composition can have a DOI of greater than 50, such as greater than 55, greater than 60, greater than 65, greater than 70, or greater than 75. In some aspects, the injection molded article has a DOI of 50 to 99.9, such as 55 to 90, 60 to 85, 65 to 80, or 70 to 75. For the upper limit, the DOI is less than 99.9, such as less than 99, less than 95, less than 90, less than 85, less than 80, or less than 75. Values close to 100 mean smoother and glossier surfaces as measured by the Byk Gardner Wave Scan meter.

In some embodiments, injection molded articles made from the polyamide composition can have a high R value as measured by a Byk Gardner Wavescan instrument. The injection molded article has an R value greater than 5, such as greater than 5.2, greater than 5.4, greater than 5.6, greater than 5.8, greater than 6.0, greater than 6.2, greater than 6.4, or greater than 6.5. In some aspects, the injection molded article has an R value of 5 to 11, e.g., 5.5 to 10.5, 6.2 to 9, 6.4 to 8.5, or 6.5 to 7.5. For the upper limit, the R value is less than 11, such as less than 10.5, less than 10, less than 9.5, or less than 9.0.

In some embodiments, injection molded articles made from the polyamide composition can have a long wavelength of 5 to 20, e.g., 6 to 18, 7 to 16, 8 to 15, 9 to 14, 10 to 13.5, or 10.5 to 13, as measured by a Byk Gardner Wavescan instrument. In terms of an upper limit, the injection molded article made from the polyamide composition may have a long wave of less than 20, such as less than 19, less than 18, less than 17, less than 16, or less than 15. With respect to the lower limit, the injection molded article made from the polyamide composition may have a long wave of more than 5, such as more than 5.5, more than 6, more than 6.5, more than 7, more than 7.5, more than 8, more than 8.5 or more than 9.

Injection molded article with metal plating

The polyamide compositions described herein can be used to form injection molded articles that can be used in a variety of applications. In general, injection molded articles can be formed by injection molding the polyamide composition and subsequently removing the molded article from the mold and cooling. In some embodiments, a method of making an injection molded article comprises: providing any of the polyamide compositions described herein; heating the polyamide composition; filling the mold cavity with a heated polyamide composition; and cooling the heated polyamide composition to form the injection molded article.

It is possible to coat thermoplastic polymers with metals. Such coatings are used for aesthetic purposes, e.g. chrome plating, for improving the mechanical properties of injection molded articles, and for improving other properties, such as electromagnetic shielding. The metal coating is preferably strongly bonded to the surface of the polymer so that the coating is not easily removed or damaged in normal use. It has been found that the use of etchable fillers, such as magnesium hydroxide, coated with a silane coupling agent improves the peel strength of injection molded articles formed from polyamide compositions. In particular, the vinyl silane coating on the etchable filler provides a polymer composition with higher peel strength compared to conventionally plated injection molded articles.

The strength of the bond between the metal coating and the injection molded article can be determined by measuring the peel strength of the metal-polymer interface. The peel strength/adhesion between polyamide compositions and metals coated on the polymers has traditionally been used only for decorative/aesthetic applications due to their poor adhesion properties. Increasing the peel strength/adhesion between the substrate and the deposited metal enables the metal coated polyamide articles to be used in higher performance applications.

In some embodiments, the polyamide compositions described herein form injection molded articles that can be metallized. Various methods can be used to place the metal on the injection molded article, such as electroless metal deposition, electrolytic plating, vacuum metallization, various sputtering methods, lamination of metal foils onto thermoplastics, and the like. In some embodiments, a method of plating an injection molded article comprises etching a filled thermoplastic resin substrate with a dilute acid solution, treating with a sensitizer such as a tin salt, activating with a noble metal salt solution, electrolessly depositing a metal using an electroless copper or nickel plating solution, and electrolytically plating with a metal selected from copper, nickel, chromium, or combinations thereof.

Conventionally, chromium has been plated from aqueous chromic acid baths that include chromium in the hexavalent form. Other polymer compositions, such as ABS and PC/ABS, require the use of hexavalent chromium to etch out butadiene in preparation for chrome plating applications. In this process, the chromic acid mist carried over by the hydrogen evolution poses a significant health hazard. The Center for Disease Control (CDC) has long recognized hexavalent chromium as a recognized carcinogen resulting from exposure to high concentrations of airborne hexavalent chromium during certain applications, such as electroplating, welding, and chrome plating. Furthermore, the chromium concentration in these baths is so high that there is a problem of waste or recycling due to so-called "carry-out" of chromium compounds into the rinse tank after the plating bath.

It has been found that injection molded articles formed from the polyamide compositions described herein can be etched with solutions that are free of toxic or carcinogenic materials, such as hexavalent chromium.

Generally, the process of coating or plating a polyamide article with a metal comprises several steps. In some embodiments, the polyamide surface is treated by etching the surface of the injection molded article with an etching solution. The etching solution can comprise an acid, such as an acid solution, a dilute acid solution, a concentrated acid mixture, or a mixture thereof. In some aspects, when using the polyamide compositions of the present disclosure, carcinogenic materials, such as hexavalent chromium, are not used in the etching solution. The polymer surface preparation may include other steps in addition to etching. After etching, the etched surface of the injection molded article is plated with a metal comprising one or more of copper, manganese, tin, nickel, iron, chromium, zinc, gold, platinum, cobalt, phosphorus, aluminum, and alloys thereof. In some aspects, the etched surface of the injection molded article is plated with chromium.

In some embodiments, the surface of the injection molded article treated with the etching solution is activated with metal ions and then electrolessly plated with metal. The last step is the electrolytic plating of a metal onto the surface of the injection molded article. Certain steps are generally carried out sequentially, in which case it is advantageous to carry out a pre-treatment or post-treatment (such as washing, cleaning, drying, heating and partial or complete neutralization of extreme pH) during these operations, optionally while agitating or subjecting the treatment solution to ultrasound. In some embodiments, the polyamide compositions disclosed herein can be plated using an etching solution that contains low amounts (if any) of hexavalent chromium.

Advantageously, the polyamide composition is also made into an injection molded article having improved peel strength between the article and the metal coating. In some embodiments, injection molded articles made from the polyamide compositions described herein have sufficient adhesion so that they do not separate from the thermoplastic substrate during use. The resulting plated article exhibits a mirror finish and high peel strength. In some aspects, the injection molded article is metallized, the metal comprising at least one of copper, manganese, tin, nickel, iron, chromium, zinc, gold, platinum, cobalt, phosphorus, aluminum, and alloys of these metals.

In some embodiments, the metal coating may comprise at least one metal in elemental form, an alloy thereof, or a metal matrix composite. The coating can be applied layer-by-layer and can have a thickness of 1 micron to 50 microns, such as 2 microns to 48 microns, 5 microns to 45 microns, 10 microns to 42 microns, 15 microns to 40 microns, 18 microns to 38 microns, 20 microns to 36 microns, 25 microns to 35 microns, 26 microns to 34 microns, or 28 microns to 32 microns. In some aspects, the coating has a thickness of less than 50 microns, such as less than 48 microns, less than 46 microns, less than 44 microns, less than 42 microns, less than 40 microns, less than 38 microns, or less than 35 microns. In some aspects, the coating has a thickness greater than 1 micron, such as greater than 2 microns, greater than 5 microns, greater than 8 microns, greater than 10 microns, greater than 20 microns, or greater than 25 microns.

In some aspects, it may be useful to apply more than one layer of different metals in combination, which may provide desirable advantages. For example, a more ductile metal such as copper may be used for the first layer, and a stronger metal such as palladium, nickel, iron, cobalt, tin, or other metals or alloys thereof may be used for the outer layer due to their strength and hardness. In some aspects, the injection molded article can be coated with multiple layers comprising one or more of palladium, nickel, electroless nickel, copper, electroless copper, and chromium. In some aspects, the injection molded article can be provided with a palladium based layer (palladium base) and treated, e.g., coated, with one or more of nickel, electroless nickel, copper, or chromium.

In some aspects, the polyamide composition can include a copolymer comprising PA-6,6 and PA-6I, wherein the composition includes glass fibers having an average diameter of 4 μ ι η to 8 μ ι η, wherein the composition has 1.3g/cm³To 1.6g/cm³Wherein the composition has an image distinctness of greater than 65 as measured by a Byk Gardner Wave Scan instrument, wherein the composition has an R value of greater than 7 as measured by a Byk Gardner Wave Scan instrument.

In some aspects, the polyamide composition can include a terpolymer comprising PA-6, PA-6I, and PA-6, wherein the composition includes glass fibers having an average diameter of 4 μm to 8 μm, wherein the composition has 1.3g/cm³To 1.6g/cm³Wherein the composition has an image distinctness of greater than 65 as measured by a Byk Gardner Wave Scan instrument, wherein the composition has an R value of greater than 7 as measured by a Byk Gardner Wave Scan instrument.

Injection molded articles made from the polyamide composition have a low extinction (dullness) as measured by a Byk Gardner Wavescan instrument. In some embodiments, the injection molded article has an extinction of 1 to 80, e.g., 2 to 60, 3 to 50, 4 to 40, 5 to 30, 6 to 20, or 7 to 15. With respect to the upper limit, the injection molded article has an extinction of less than 80, such as less than 70, less than 60, less than 50, less than 40, less than 30, less than 25, less than 20, or less than 10. With respect to the lower limit, the injection molded article has an extinction of greater than 1, such as greater than 2, greater than 3, greater than 4, greater than 5, greater than 6, greater than 7, greater than 8, or greater than 9.

Applications requiring high peel strength include electrical and electronic components, Personal Digital Assistants (PDAs), cellular and mobile phone components, notebook computer components and the like, automotive components, aerospace components, defense components, consumer products, medical components, and sporting goods. Suitable components include pipes or shafts used in sporting goods such as ski and hiking poles, fishing rods, golf clubs, hockey sticks, lacrosse sticks, baseball/softball sticks, bicycle frames, ice skates, skis. Other applications include panels such as golf club head panels and complex shapes such as sports racquets (tennis balls, racquetball (racquetball), squash balls, etc.), golf club heads, automotive protective grilles, foot pedals such as brake and accelerator pedals, fuel rails, running boards, spoilers, muffler tips, wheels (wheels), vehicle frames, structural supports, and the like. An article whose surface is to be coated with a metal can be formed by: the polymer composition is injection molded, and the molded article is subsequently removed from the mold and cooled.

Examples

Examples 1 and 2 were prepared by blending the following components in the amounts shown in table 1:

PA-6,6/6I containing 6% by weight of PA-6, I (example 1) or PA-6/6I/6 containing 10% by weight of PA-6I and 6% by weight of PA-6 (example 2);

glass fibers, NEG T-289DE from Nippon Electric-round cross section glass fibers (E-glass fibers with a diameter of 6.5 microns);

vinylsilane-coated magnesium hydroxide, i.e. fromOf Magnifin GmbH in BergheimH-10A (etchable filler);

nigrosine pigment from Orient Chemicals (NA-143);

zinc stearate (additive) (NA-095); and

NYLOSABA S-EED (hindered amine stabilizer (additive) sold by Clariant GmbH, Augsburg, Germany and described as 1, 3-benzenedicarboxamide, N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl))

An injection molded article is formed according to the methods discussed herein. The injection molded articles exhibit an excellent combination of aesthetic properties and improved structural properties compared to injection molded articles formed from conventional polyamide compositions.

Examples 3-5 and comparative examples A-H were prepared by blending the following components in the amounts shown in Table 2. Examples 3-5 contain polyamide, etchable filler and glass fibers with low average median diameter, for example, up to 10 microns (6.5 microns). Comparative examples a-E include glass fibers having a high average median diameter, e.g., greater than 10 microns. Comparative examples F-H did not contain any etchable filler. The polyamide composition is used for producing an injection molded polyamide article. Weight percentages are based on the total weight of the polyamide composition, unless otherwise indicated. The injection molded articles were tested for aesthetic and physical properties. The results are shown in tables 3 and 4.

The semi-structural mineral used in comparative example F was POLARITE 902A and that used in comparative examples G & H was POLARITE 702A

"MDH-VS" refers to a vinyl silane coated magnesium hydroxide

"S-EED" refers to NYLOSABA S-EED.

As shown in table 3, the combination of polyamide, type and size of glass fiber and amount of etchable filler in a synergistic combination improves the surface appearance of the respective injection molded article. For example, examples 3-5 each exhibited an R value greater than 6 and a DOI greater than 68.

In contrast, comparative examples A-E produced injection molded articles having very poor surface appearances, e.g., R values less than 5 and DOI less than 50. As for comparative examples F-H, the surface appearance was even worse and often too dull to measure. Although comparative examples F-H contained glass fibers having an average median diameter of less than 10 microns, these comparative examples did not contain any etchable filler. In addition, comparative example a, which contained PA6,6/6 copolymer and did not include any PA6, I, exhibited poor surface appearance.

As shown in table 4, examples 3-5 also exhibited good mechanical properties. Examples 3-5 contained PA6/6, I copolymer having about 15 wt.% PA6, I and glass fibers having an average median diameter of about 6.5 microns. Examples 3-5 exhibited tensile strengths greater than 125MPa and flexural strengths greater than 8000 MPa.

Although comparative examples E-H achieved moderate/good physical properties, the surface appearance properties of injection molded articles formed from these polyamide compositions were very poor. As shown in tables 3 and 4, the injection molded articles formed from the polyamide compositions of examples 3-5 surprisingly achieved moderate/good surface appearance properties while maintaining most of the mechanical properties desirable for injection molded articles.

Detailed description of the preferred embodiments

The following embodiments are contemplated. All combinations of features and embodiments are contemplated.

Embodiment 1A polyamide composition comprising: 40 to 80 weight percent of a polyamide; 0.5 to 40 weight percent of an etchable filler; 5 to 30 weight percent glass fiber; optionally less than 40 wt% semi-structural minerals; and optionally from 0.1 wt% to 13 wt% of an additive.

Embodiment 2 the embodiment of embodiment 1 wherein the polyamide comprises a terpolymer of PA-6, PA4,6, PA-6,9, PA-6,10, PA-6,12, PA11, PA12, PA9,10, PA9,12, PA9,13, PA9,14, PA9,15, PA-6,16, PA9,36, PA10,10, PA10,12, PA10,13, PA10,14, PA12,10, PA12,12, PA12,13, PA12,14, PA-6,13, PA-6,15, PA-6,16, PA-6,13, PAMXD,6, PA4T, PA5T, PA-6T, PA-T, PA10T, PA-T, and mixtures thereof.

Embodiment 3 the embodiment of any of embodiments 1 or 2 wherein the polyamide is a copolymer comprising PA-6,6 and PA-6I.

Embodiment 4 the embodiment of embodiment 3 wherein the copolymer comprises 2 to 20 weight percent PA-6I.

Embodiment 5 the embodiment of any of embodiments 1 or 2 wherein the polyamide is a terpolymer comprising PA-6, PA-6 and PA-6I.

Embodiment 6 the embodiment of embodiment 5 wherein the terpolymer comprises 2 to 20 weight percent PA-6I and 2 to 20 weight percent PA-6.

Embodiment 7 an embodiment of any of the preceding embodiments, wherein the additive comprises at least one of: inorganic stabilizers, organic stabilizers, flame retardants, lubricants, dyes, pigments, nucleating agents, metal flakes, impact modifiers, antistatic agents, conductivity additives, mold release agents, optical brighteners, adhesion promoters, aging inhibitors, antioxidants, antiozonants, light stabilizers, ultraviolet absorbers, ultraviolet blockers, inorganic heat stabilizers, organic heat stabilizers, processing aids, crystallization promoters, crystallization retarders, flow aids, fibrous materials, and particulate fillers.

Embodiment 8 the embodiment of embodiment 7 wherein the additive comprises 1 to 10 weight percent pigment, 0.05 to 1 weight percent lubricant, and/or 0.25 to 2 weight percent processing aid.

Embodiment 9 the embodiment of embodiment 7 or 8 wherein the pigment comprises thermally stable nigrosine.

Embodiment 10 the embodiment of embodiment 7 or 8 wherein the lubricant comprises zinc stearate.

Embodiment 11 an embodiment of embodiment 7 or 8 wherein the processing aid comprises a substituted piperidine compound.

Embodiment 12 an embodiment of any of the preceding embodiments, wherein the etchable filler is coated with an organosilane coating.

Embodiment 13 embodiment 12 wherein the organosilane coating comprises a vinyl silane.

Embodiment 14 embodiment 12 wherein the organosilane coating comprises an aminosilane.

Embodiment 15 the embodiment of any of the preceding embodiments, wherein the etchable filler comprises one or more of magnesium hydroxide, calcium carbonate, and wollastonite.

Embodiment 16 the embodiment of any of the preceding embodiments, wherein the glass fibers have an average diameter of less than 10 microns.

Embodiment 17 the embodiment of any of the preceding embodiments, wherein the glass fibers have an average diameter of 4 to 8 microns.

Embodiment 18 the embodiment of any of the preceding embodiments, wherein the composition comprises a semi-structural mineral, wherein the semi-structural mineral comprises one or more of kaolin, mica, talc, and wollastonite.

Embodiment 19 an embodiment of any of the preceding embodiments, wherein the composition has an image distinctness of image of greater than 65 as measured by a Byk Gardner Wave Scan meter.

Embodiment 20 an embodiment of any of the preceding embodiments, wherein the composition has an R-value of greater than 7 as measured by a Byk Gardner Wave Scan meter.

Embodiment 21 an embodiment of any of the preceding embodiments, wherein the composition has 1.25g/cm³To 1.6g/cm³The density of (c).

Embodiment 22 an embodiment of any of the preceding embodiments, wherein the composition has a melting point of 220 ℃ to 260 ℃.

Embodiment 23 embodiment of any of the preceding embodiments, wherein the polyamide is a copolymer comprising PA-6,6 and PA-6I, wherein the composition comprises glass fibers having an average diameter of 4 microns to 8 microns, wherein the composition has 1.3g/cm³To 1.6g/cm³Wherein the composition has an image distinctness of greater than 65 as measured by a Byk Gardner Wave Scan instrument, wherein the composition has an R value of greater than 7 as measured by a Byk Gardner Wave Scan instrument.

Embodiment 24 the embodiment of any of the preceding embodiments, wherein the polyamide is a terpolymer comprising PA-6, PA-6I, and PA-6, wherein the composition comprises glass fibers having an average diameter of 4 microns to 8 microns, wherein the composition has 1.3g/cm³To 1.6g/cm³Wherein the composition has an image distinctness of greater than 65 as measured by a Byk Gardner Wave Scan instrument, wherein the composition has an R value of greater than 7 as measured by a Byk Gardner Wave Scan instrument.

Embodiment 25 an injection molded article formed from the composition of any of the preceding embodiments.

Embodiment 26 the embodiment of embodiment 25 wherein the injection molded article is metal plated, the metal comprising one or more of copper, manganese, tin, nickel, iron, chromium, zinc, gold, platinum, cobalt, phosphorus, aluminum, and alloys thereof.

Embodiment 27 an embodiment of embodiment 26, wherein the injection molded article is chrome plated.

Embodiment 28A polyamide composition comprising: 40 to 80 weight percent of a polyamide; 0.5 to 40 weight percent silane coated magnesium hydroxide; 5 to 30 wt% of glass fibers having a diameter of less than 10 microns; optionally less than 40% by weight kaolin; and optionally from 0.1 wt% to 13 wt% of an additive.

Embodiment 29 embodiment of embodiment 28 wherein the additives comprise at least one of inorganic stabilizers, organic stabilizers, flame retardants, lubricants, dyes, pigments, nucleating agents, metal flakes, impact modifiers, antistatic agents, conductivity additives, mold release agents, fluorescent whitening agents, adhesion promoters, aging inhibitors, antioxidants, antiozonants, light stabilizers, ultraviolet light absorbers, ultraviolet light blockers, inorganic heat stabilizers, organic heat stabilizers, processing aids, crystallization promoters, crystallization retarders, flow aids, fibrous materials, and particulate fillers.

Embodiment 30 the embodiment of embodiment 28 or 29 wherein the additive comprises 1 to 10 weight percent nigrosine, 0.05 to 1 weight percent zinc stearate, 0.25 to 2 weight percent nylosab S-EED.

Embodiment 31 a method of making an injection molded article comprising: provided is a polyamide composition comprising: 40 to 80 weight percent of a polyamide; 0.5 to 40 weight percent of an etchable filler; 5 to 30 weight percent glass fiber; optionally less than 40 wt% semi-structural minerals; and optionally from 0.1 wt% to 13 wt% of an additive; heating the polyamide composition; filling the mold cavity with a heated polyamide composition; cooling the heated polyamide composition to form the injection molded article.

Embodiment 32 the embodiment of embodiment 31, further comprising etching the surface of the injection molded article with an etching solution.

Embodiment 33 the embodiment of any one of embodiments 31 or 32 wherein the etching solution does not comprise any hexavalent chromium.

Embodiment 34 the embodiment of any of embodiments 31 to 33, further comprising plating the etched surface of the injection molded article with a metal comprising one or more of copper, manganese, tin, nickel, iron, chromium, zinc, gold, platinum, cobalt, phosphorus, aluminum, and alloys thereof.

Embodiment 35 the embodiment of any of embodiments 31 to 34, wherein the etched surface of the injection molded article is plated with chromium.

Embodiment 36 the embodiment of any one of embodiments 31 to 35 wherein the additive comprises at least one inorganic stabilizer, organic stabilizer, flame retardant, lubricant, dye, pigment, nucleating agent, metal flake, impact modifier, antistatic agent, conductivity additive, mold release agent, optical brightener, adhesion promoter, aging inhibitor, antioxidant, antiozonant, light stabilizer, ultraviolet absorber, ultraviolet blocker, inorganic heat stabilizer, organic heat stabilizer, processing aid, crystallization promoter, crystallization retardant, flow aid, fibrous material, and particulate filler.

Embodiment 37 a polyamide composition comprising: 40 to 80 weight percent of a polyamide; 0.5 to 40 weight percent of an etchable filler; 5 to 30 wt% of glass fibers having an average diameter of at most 10 microns; less than 40% by weight of semi-structural minerals; and 0.1 to 13% by weight of an additive.

Embodiment 38 is the embodiment of embodiment 37 wherein the polyamide comprises a terpolymer of PA-6, PA4,6, PA-6,9, PA-6,10, PA-6,12, PA11, PA12, PA9,10, PA9,12, PA9,13, PA9,14, PA9,15, PA-6,16, PA9,36, PA10,10, PA10,12, PA10,13, PA10,14, PA12,10, PA12,12, PA12,13, PA12,14, PA-6,13, PA-6,15, PA-6,16, PA-6,13, PAMXD,6, PA4T, PA5T, PA-6T, PA-T, PA10T, PA-T, and mixtures thereof.

Embodiment 39 the embodiment of any one of embodiments 37 or 38 wherein the polyamide is a copolymer comprising PA-6,6 and PA-6I wherein PA-6I is 2 to 20 weight percent.

Embodiment 40 the embodiment of any of embodiments 37 or 38 wherein the polyamide is a terpolymer comprising PA-6, PA-6 and PA-6I wherein the terpolymer comprises from 2 to 20 weight percent PA-6I and from 2 to 20 weight percent PA-6.

Embodiment 41 the embodiment of any one of embodiments 37 to 40 wherein the additive comprises at least one of: inorganic stabilizers, organic stabilizers, flame retardants, lubricants, dyes, pigments, nucleating agents, metal flakes, impact modifiers, antistatic agents, conductivity additives, mold release agents, optical brighteners, adhesion promoters, aging inhibitors, antioxidants, antiozonants, light stabilizers, ultraviolet absorbers, ultraviolet blockers, inorganic heat stabilizers, organic heat stabilizers, processing aids, crystallization promoters, crystallization retarders, flow aids, fibrous materials, and particulate fillers.

Embodiment 42 the embodiment of any of embodiments 37-41, wherein the additive comprises 1 to 10 weight percent of a pigment, 0.05 to 1 weight percent of a lubricant, and/or 0.25 to 2 weight percent of a processing aid, wherein the pigment comprises thermally stable nigrosine, wherein the lubricant comprises zinc stearate, and wherein the processing aid comprises a substituted piperidine compound.

Embodiment 43 the embodiment of any one of embodiments 37-42, wherein the polyamide composition comprises 0.5 wt% to 25 wt% etchable filler, and wherein the etchable filler is coated with one or more of an organosilane coating, a vinylsilane coating, or an aminosilane coating.

Embodiment 44 the embodiment of any one of embodiments 37 to 43 wherein the etchable filler comprises one or more of magnesium hydroxide, calcium carbonate, and wollastonite.

Embodiment 45 the embodiment of any of embodiments 37-44, wherein the glass fibers have an average diameter of 4 to 8 microns.

Embodiment 46 the embodiment of any one of embodiments 37 to 45 wherein the composition comprises a semi-structural mineral, wherein the semi-structural mineral comprises one or more of kaolin, mica, talc and wollastonite.

Embodiment 47 the embodiment of any one of embodiments 37 to 46 wherein the composition has an image distinctness of greater than 50 as measured by a Byk Gardner Wave Scan meter, and wherein the composition has an R-value of greater than 5 as measured by a Byk Gardner Wave Scan meter.

Embodiment 48 the embodiment of any of embodiments 37 to 47, wherein the composition has 1.25g/cm³To 1.6g/cm³And wherein the composition has a melting point of 220 ℃ to 260 ℃.

Embodiment 49 embodiment of any of embodiments 37-39 and 41-48, wherein the polyamide is a copolymer comprising PA-6,6 and PA-6I, wherein the composition comprises glass fibers having an average diameter of 4 microns to 8 microns, wherein the composition has 1.3g/cm³To 1.6g/cm³Wherein the composition has an image distinctness of greater than 65 as measured by a Byk Gardner Wave Scan instrument, wherein the composition has an R value of greater than 7 as measured by a Byk Gardner Wave Scan instrument.

Embodiment 50 embodiment of any of embodiments 37, 38, and 40-48, wherein the polyamide is a terpolymer comprising PA-6, PA-6I, and PA-6, wherein the composition comprises glass fibers having an average diameter of 4 microns to 8 microns, wherein the composition has 1.3g/cm³To 1.6g/cm³Wherein the composition has an image distinctness of greater than 65 as measured by a Byk Gardner Wave Scan instrument, wherein the composition has an R value of greater than 7 as measured by a Byk Gardner Wave Scan instrument.

Embodiment 51 an injection molded article formed from the composition of any of embodiments 37-50, wherein the injection molded article is metal plated, the metal comprising one or more of copper, manganese, tin, nickel, iron, chromium, zinc, gold, platinum, cobalt, phosphorus, aluminum, and alloys thereof.

Embodiment 52A polyamide composition comprising: 40 to 80 weight percent of a polyamide; 0.5 to 40 weight percent silane coated magnesium hydroxide; 5 to 30 wt% of glass fibers having an average diameter of at most 10 microns; less than 40% by weight kaolin; and 0.1 to 13% by weight of an additive.

Embodiment 53 the embodiment of embodiment 52 wherein the additive comprises 0.5 to 10 weight percent of thermally stable nigrosine, 0.05 to 1 weight percent of zinc stearate, and/or 0.25 to 2 weight percent of a substituted piperidine compound.

Embodiment 54 a method of making an injection molded article, comprising: provided is a polyamide composition comprising: 40 to 80 weight percent of a polyamide; 0.5 to 40 weight percent of an etchable filler; 5 to 30 wt% of glass fibers having an average diameter of at most 10 microns; less than 40% by weight of semi-structural minerals; and 0.1 to 13 weight percent of an additive; heating the polyamide composition; filling the mold cavity with a heated polyamide composition; cooling the heated polyamide composition to form the injection molded article.

Embodiment 55 the embodiment of embodiment 54 further comprising etching the surface of the injection molded article with an etching solution, wherein the etching solution does not comprise any hexavalent chromium.

Embodiment 56 the embodiment of any of embodiments 54 or 55 further comprising plating the etched surface of the injection molded article with a metal comprising one or more of copper, manganese, tin, nickel, iron, chromium, zinc, gold, platinum, cobalt, phosphorus, aluminum, and alloys thereof.

Although the present disclosure has been described in detail, modifications within the spirit and scope of the present disclosure will be readily apparent to those of ordinary skill in the art. Based on the above discussion, relevant knowledge in the art, and references discussed above in connection with the background and detailed description (the disclosures of which are all incorporated herein by reference). Furthermore, it should be understood that embodiments and portions of the various embodiments of the present disclosure and various features recited below and/or in the appended claims may be combined or interchanged either in whole or in part. In the above description of various embodiments, those embodiments relating to another embodiment may be combined with other embodiments as appropriate, as recognized by one of ordinary skill in the art.