Nanocomposite compositions of polyamides and sepiolite-type clays

The present invention directs nanocomposites containing thermoplastic polyamides and unmodified sepiolite-type clay nanoparticles. The present invention also includes articles made of nanocomposites.

Nanocomposites are compositions that meet many of the challenges currently presented by automotive plastics and composites. These materials offer a variety of desirable properties, including low coefficient of thermal expansion, high thermal deformation temperature, light weight, improved scratch resistance, and good appearance. Nanocomposite compositions are polymers reinforced with nanometer-sized particles (nanoparticles), that is, particles typically sized to about one to several hundred nanometers. These materials can be used, among other things, for structural, semi-structured, high heat underhoods, and Class A automotive components. In other words, these nanocomposites are compositions in which small particles are dispersed in a plastic matrix.

Injection-moldable thermoplastics have long been mechanically fortified with the addition of microparticles and fiber fillers to improve mechanical properties such as stiffness, dimensional stability, and temperature resistance. Typical fillers include chopped fiberglass and talc, which are added at a filler usage of 20-40% to obtain significant mechanical reinforcement. However, at these usage levels, cold impact performance and material toughness are usually sacrificed. Polymer-silicate nanocomposites, in other words compositions in which the silicates are dispersed as very small particles, can address these issues.

Polymer layered silicate nanocomposites typically incorporate layered clay mineral fillers in the polymer matrix. Layered silicates consist of hundreds of thin plate layers stacked in regular bundles known as the mitotic spindle. Each of these platelets is characterized by a large aspect ratio (diameter / thickness of about 100-1000). Thus, when the clay is uniformly dispersed and stripped as individual platelets throughout the polymer matrix, strength, flexural modulus and Young's modulus, and thermal deformation due to the large surface contact between the polymer and the filler. A dramatic increase in temperature is observed with very low filler usage (less than 10% by weight).

Clay minerals and their industrial uses have been reviewed in (Non-Patent Document 1). Two types of clay minerals: kaolin and smectite are commonly used in nanocomposites. Kaolin molecules are located on two sheets or plates, one on silica and one on alumina. The most widely used smectites are sodium montmorillonite and calcium montmorillonite. Smectite is located on two silica sheets and one alumina sheet. The molecules of montmorillonite clay minerals are not as tightly bound as those of the kaolin group and are therefore far apart.

Polyamide nanocomposites typically combine polyamide with an inorganic layered silicate, usually smectite clay. Alkaline and alkaline earth metal ions in layered silicates are onium ions, typically alkylammonium from alkylammonium salts (eg octadecylammonium chloride or quaternary ammonium tallow) to facilitate insertion and subsequent exfoliation. It is exchanged for ions, or ω-amino acids (eg, 12-aminolauric acid). Clays so treated are often referred to as "(organically) modified clays" or "organic clays". However, these compounds are not sufficiently thermally stable to be used with their high temperature blended polyamides, especially semi-aromatic polyamides.

Polyamide nanocomposites have been prepared by melt blending (also referred to as "melt mixing"). In (Patent Document 1), Oda et al. Dissolved 15 and 30% by weight of sepiolite in polyamide 6 after drying sepiolite at 100 ° C for 24 hours. It describes the fiber diameter of sepiolite, usually about 0.05-0.3 μm, and the fiber length of about 1-100 μm. No specific restrictions on the fiber diameter or length of sepiolite are disclosed, but sepiolite with a fiber diameter of about 0.1-0.2 μm and a fiber length of about 3-30 μm is readily available and provides excellent results. Is disclosed. It is also disclosed that the use of less than 5% by weight sepiolite does not achieve improved mechanical strength, heat resistance and warpage properties.

<patcit num="1"><text>Japanese Unexamined Patent Publication No. 2-182758</text></patcit><patcit num="2"><text>European Patent Application Publication No. 0454222A</text></patcit><patcit num="3"><text>European Patent Application Publication No. 0170299A</text></patcit><patcit num="4"><text>U.S. Pat. No. 2,071,250</text></patcit><patcit num="5"><text>U.S. Pat. No. 2,071,251</text></patcit><patcit num="6"><text>U.S. Pat. No. 2,130,523</text></patcit><patcit num="7"><text>U.S. Pat. No. 2,130,948</text></patcit><patcit num="8"><text>U.S. Pat. No. 2,241,322</text></patcit><patcit num="9"><text>U.S. Pat. No. 2,312,966</text></patcit><patcit num="10"><text>U.S. Pat. No. 2,512,606</text></patcit><patcit num="11"><text>U.S. Pat. No. 3,393,210</text></patcit><patcit num="12"><text>U.S. Pat. No. 5,378,800</text></patcit><patcit num="13"><text>U.S. Pat. No. 5,322,923</text></patcit><patcit num="14"><text>U.S. Pat. No. 5,424,104</text></patcit><patcit num="15"><text>US Reissue Patent No. 34,447</text></patcit><patcit num="16"><text>U.S. Pat. No. 6,140,459</text></patcit><patcit num="17"><text>U.S. Pat. No. 4,174,358</text></patcit><patcit num="18"><text>U.S. Pat. No. 5,112,908</text></patcit><nplcit num="1"><text>HM Murray, Applied Clay Science 17 (2000), pp. 207-221</text></nplcit><nplcit num="2"><text>Polymer International 53 (2004), pp. 1060-1065</text></nplcit><nplcit num="3"><text>HF Mark, edited by JI Kroschwitz, Encyclopedia of Polymer Science and Technology, 2nd Edition, Vol. 8, pp. 393-396</text></nplcit><nplcit num="4"><text>Li, D. (Li, D.), E, AF (Yee, AF), Powers, KW (Powers, KW) Wang, HC (Wang, HC), Yu, TC (Yu, TC), Polymer 34 ( 1993), page 4471</text></nplcit>

<p num="0009"> For the reasons mentioned above, there is a need for improved polyamide nanocomposites with low concentrations of nanoparticles that can be processed at high temperatures and provide improved properties. The present invention meets this need.</p>

<p num="0010"> The present invention directs nanocomposite compositions comprising at least one thermoplastic polyamide and unmodified sepiolite-type clay nanoparticles, each having a particle width and thickness of less than 50 nm.</p>

The present invention relates to a nanocomposite composition containing at least one thermoplastic polyamide and unmodified sepiolite-type clay nanoparticles. The present invention includes articles containing such compositions. As used herein, the term "nanocomposite" or "polymer nanocomposite" or "nanocomposite composition" is a polymeric material containing nanoparticles dispersed throughout the polymeric material. Means a polymeric material in which nanoparticles have at least one dimension less than 50 nm (nanoparticles). The term "polyamide composite" means a nanocomposite in which the polymeric material comprises at least one polyamide.

Where a series of numbers are listed herein, this range is intended to include its endpoints, as well as all integers and fractions within this range, unless otherwise stated. It is not intended that the scope of the invention be limited to the specific values listed when defining the scope.

(Sepiolite type clay) As used herein, the term "sepiolite-type clay" means both sepiolite and attapargite (parigolite) clays and mixtures thereof.

Sepiolite-type clay is a layered fibrous material composed of two sheets of regular tetrahedral silica units in which each layer is bonded to a central sheet of regular octahedral units containing magnesium ions (for example, (Non-Patent Document 2)). Please refer to).

Sepiolite (Mg₄Si₆O₁₅(OH)₂ 6 (H₂O) is a hydrated magnesium silicate filler that exhibits a high aspect ratio due to its fibrous structure. Unique among silicates, sepiolite consists of long lath-like crystals with silica chains running parallel to the fiber axis. This material has been shown to consist of two forms, the α and β forms. The α form is known to be a long bundle of fibers, and the β form exists as an amorphous aggregate.

Attapargite (also known as parigolite) is structurally and chemically identical to sepiolite, except that attapargite has slightly smaller unit cells. As used herein, the term "sepiolite-type clay" includes not only sepiolite itself but also sepiolite.

Sepiolite-type viscous is available in high-purity, non-denatured form (eg, Pangel® S-9 sepiolite clay from Tolsa Group, Madrid, Spain). ). Preferably the clay is in the form of fine particles, so it may be easily dispersed in the polyamide melt.

The sepiolite clay used in the compositions described herein is unmodified. The term "undaturated" means that the surface of sepiolite-type clay was not treated with an organic compound such as an onium compound (eg, to make the surface less polar).

The width (x) and thickness (y) of sepiolite-type clay fibers contained in the compositions described herein are less than 50 nm, respectively (Fig. 1). The length (z) of sepiolite-type fibers is also illustrated in FIG. In certain embodiments, sepiolite clays are rheological additives such as those described in (Patent Document 2) and (Patent Document 3) and marketed by Torsa, Madrid, Spain under the Trademark Panger®. It is a grade. As stated in them, the "rheology additive grade" is 120m²/ g (N₂, BET) Larger specific surface area, and typical fiber dimensions: sepiolite-type clays 200-2000 nm long, 10-30 nm wide, and 5-10 nm thick.

Rheological additive grade sepiolite is obtained from natural sepiolite using a special ultra-fine milling method that substantially prevents the destruction of sepiolite fibers so that sepiolite is easily dispersed in water and other polar liquids, and is highly impaired. Regularity and 300m²It has an outer surface with a high specific surface area of more than / g and a high density active center for adsorption that gives it a very high water retention capacity when hydrogen bonds can be formed relatively easily with the active center. The microfibrous nature of the rheological additive grade sepiolite nanoparticles makes sepiolite a material with high pore space and low apparent density.

In addition, rheology additive grade sepiolite has a very low cation exchange capacity (10-20 eq / 100 g) and has a very weak interaction with the electrolyte, which in turn leads to rheology additive grade sepiolite. Is substantially unaffected by the presence of salts in the medium in which it is found, and therefore it remains stable over a wide pH range.

The above-mentioned qualities of rheology additive grade sepiolite are also in the range of ATTAGEL products manufactured and marketed by, for example, the company Engelhard Corporation, United States (eg, Atagel 40 and Atagel 50). , And the Floridin Company's MIN-U-GEL range, which can be attributed to rheology additive grade attackers with particle sizes smaller than 40 microns.

Preferably, the amount of sepiolite-type clay used in the present invention is about 0.1 to about 30% by weight, most preferably about 0.1 to about 4% by weight, based on the total amount of sepiolite-type clay and polyamide in the final composition. The range. The specific amount chosen will depend on the intended use of the nanocomposite composition, as is well understood in the art. For example, in films, it may be advantageous to use as little sepiolite-type clay as possible to retain the desired optical properties. A "masterbatch" of nanocomposite compositions containing relatively high concentrations of sepiolite-type clay may also be used. For example, a nanocomposite composition masterbatch containing 30% by weight sepiolite clay may be used. If a composition with 3 weight percent sepiolite clay is required, the composition containing 3 weight percent should be melt-mixed 1 part by weight of 30% masterbatch with 9 parts by weight of "pure" polyamide. May be manufactured by. During this melt mixing, other desired components can be added to form the final desired composition.

(polyamide) As used herein, "polyamide" means a condensed polymer in which more than 50 percent of the groups connecting the repeating units are amide groups. Thus, the "polyamide" may include polyamides, poly (ester-amides) and poly (amide-imides) as long as more than half of the linking groups are amide groups. In one embodiment at least 70% of the linking groups are amides, in another embodiment at least 90% of the linking groups are amides and in another embodiment all of the linking groups are amides. The proportion of ester linking groups can be estimated by the first approximation based on the molar amount of the monomer used to produce the polyamide.

Suitable polyamides for use in the nanocomposites described herein include thermoplastic polyamide homopolymers, copolymers, terpolymers, or more multidimensional polymers (both block and random). As used herein, the term "thermoplastic polyamide" refers to a polyamide that can soften and flow when heated, and retain its given shape at high temperatures and cure on cooling. means. Preferably, such polyamides are aliphatic or semi-aromatic.

(Aliphatic polyamide) Aliphatic polyamides are well known in the art. Suitable polyamides include, for example, US Patent Gazette (Patent Document 4), US Patent Gazette (Patent Document 5), US Patent Gazette (Patent Document 6), US Patent Gazette (Patent Document 7), US Patent Gazette (Patent Document 7). 8), US Patent Gazette (Patent Document 8), US Patent Gazette (Patent Document 9), US Patent Gazette (Patent Document 10), and US Patent Gazette (Patent Document 11). The manufacturing method is well known in the art. For example, a polyamide resin can be produced by condensation of an equimolar amount of a saturated dicarboxylic acid containing 4 to 12 carbon atoms and a diamine containing 4 to 14 carbon atoms. Excess diamines can be used to provide excess amine end groups in the polyamide. Examples of aliphatic polyamides so produced include poly (tetramethylene adipamide) (polyamide 4,6), poly (hexamethylene adipamide) (polyamide 6,6), poly (hexamethylene azella). Amide) (Polyamide 6,9), Poly (Hexamethylene sebacamide) (Polyamide 6,10), Poly (Hexamethylene dodecanoamide) (Polyamide 6,12), Bis (Para-aminocyclohexyl) Methandodecanoamide Etc., but are not limited to them. Aliphatic polyamides can also be produced by ring-opening polymerization of lactams, such as ε-caprolactam (polycaprolactam, also known as polyamide 6) and poly-11-amino-undecanoic acid (polyamide 11). It is also possible to use polyamides produced by two copolymerizations of the above polymers or ternary copolymerization of the above polymers or their components. Examples of the polycondensation polyamide include polyamide 6/66, polyamide 6/610, polyamide 6/12, and polyamide 6/46. Among the aliphatic polyamides, polyamides 6 and 6,6 are preferable.

(Semi-aromatic polyamide) Thermoplastic semi-aromatic polyamides are particularly preferred for the nanocomposites described herein. As used herein, "semi-aromatic polyamide" means a polyamide containing both a divalent aromatic group and a divalent non-aromatic group. As used herein, "divalent aromatic group" means an aromatic group attached to another portion of a macrocyclic molecule. For example, the divalent aromatic group may include a meta- or para-bonded monocyclic aromatic group. Preferably, the free valence is for the aromatic ring carbon atom.

Semi-aromatic polyamides are well known in the art. Suitable polyamides and manufacturing methods include, for example, US Patent Gazette (Patent Document 12), US Patent Gazette (Patent Document 13), US Patent Gazette (Patent Document 14), US Patent Gazette (Patent Document 15), and US Patent Document. Those described in Japanese Patent Application Laid-Open No. 16 are included.

The thermoplastic semi-aromatic polyamide may be one or more homopolymers, copolymers, terpolymers, or more multidimensional polymers derived in part from monomers containing divalent aromatic groups. It is also a combination of one or more aliphatic polyamides and one or more homopolymers, copolymers, terpolymers, or more multidimensional polymers, partially derived from monomers containing divalent aromatic groups. It may be a blend.

Preferred monomers containing a divalent aromatic group are terephthalic acid and its derivatives, isophthalic acid and its derivatives, and m-xylylene diamine. Approximately 5 to about 75 mol% of the monomers used to produce the semi-aromatic polyamides used in the nanocomposites described herein preferably contain divalent aromatic groups and are of the monomer. More preferably, about 10 to about 55 mol% contains a divalent aromatic group. Therefore, preferably, about 5 to about 75 mole percent, or more preferably 10 to about 55 mole percent, of the repeating units of all polyamides used in the nanocomposites described herein are divalent aromatic groups. Contains.

Semi-aromatic polyamides optionally have one or more additional aliphatic dicarboxylic acid monomers or derivatives thereof, such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, and 6-20 carbon atoms. It may contain repeating units derived from other aliphatic or alicyclic dicarboxylic acid monomers. As used herein, "alicyclic" means a divalent non-aromatic hydrocarbon group containing a cyclic structure within them.

Semi-aromatic polyamides may optionally contain repeating units derived from one or more aliphatic or alicyclic diamine monomers having 4 to 20 carbon atoms. Preferred aliphatic diamines may be linear or branched, hexamethylenediamine, 2-methyl-1,5-pentanediamine, 1,8 diaminooctane, 1,9-diaminononane, methyl-1,8-diaminooctane. , 1,10-diaminodecane, and 1,12-diaminododecane. Examples of alicyclic diamines include 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,4-bis (aminomethyl) cyclohexane, and bis (p-aminocyclohexyl) methane. ..

Semi-aromatic polyamides may optionally contain repeating units derived from lactams and aminocarboxylic acids (or acid derivatives) such as caprolactam, 11-aminoundecanoic acid, and laurolactam.

Examples of preferred semi-aromatic polyamides are poly (m-xylylene adipamide) (polyamide MXD, 6), hexamethylene dipamide / hexamethylene terephthalamide copolyamide (polyamide 6, T / 6,6). , Hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide-copolyamide (polyamide 6, T / D, T), poly (dodecamethylene terephthalamide) (polyamide 12, T), poly (decamethylene terephthalamide) (polyamide) 10,T), decamethylene terephthalamide / decamethylene dodecanoamide-copolyamide (polyamide 10, T / 10,12), poly (nonamethylene terephthalamide) (polyamide 9, T), hexamethylene isophthalamide and hexamethylene Polyamide of adipamide (polyamide 6, I / 6,6); hexamethylene terephthalamide, hexamethylene isophthalamide, and polyamide of hexamethylene adipamide (polyamide 6, T / 6, I / 6,6); and Polyamides and mixtures of these polymers include.

The semi-aromatic polyamide will preferably have a melting point of at least about 280 ° C, preferably less than about 340 ° C.

Among the semi-aromatic polyamides, hexamethylene adipamide / hexamethylene terephthalamide copolyamide (polyamide 6, T / 6,6) and hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide copolyamide (polyamide 6) , T / D, T) is preferred.

(Solid fine particle filler (excluding sepiolite type clay)) As used herein, "solid particulate fillers except sepiolite-type clays" are any solids that are sufficiently subdivided to be dispersed in the composition under melt-mixing conditions (see below). Means (insoluble at the temperature at which the composition is normally exposed).

The solid particulate filler must be subdivided sufficiently to be dispersed in the composition under melt mixing conditions (see below). Typically, solid particulate fillers will be materials that may already be used in thermoplastic compositions, such as pigments, stiffeners, flame retardants, and fillers. The solid microparticle filler may or may not have a coating on it, eg, a sizing and / or coating to improve the adhesion of the solid microparticle filler to the polymer of the composition. The solid particulate filler may be organic or inorganic.

Useful specific reinforcements include kaolin clay, talc, aramid, mica, and calcium carbonate; various forms of glass such as fiber, ground glass, non-hollow or hollow spheres; carbon black or carbon fiber; Includes minerals such as titanium dioxide; aramid in the form of short fibers, fibrils or fibrils; and mixtures of two or more of these. Other reinforcements are wollastonite, mica, talc, and glass, especially fiberglass, and mixtures of two or more of these. These reinforcing agents may be coated with an adhesion promoter or other material commonly used to coat the reinforcing agents used in thermoplastics. The reinforcing agent may be present in an amount of 0 to about 60% by weight based on the total composition.

Typical flame retardants include brominated polystyrene, brominated polyphenylene oxide, red phosphorus, magnesium hydroxide, and magnesium carbonate. These are typically used with flame retardant synergists such as antimony pentoxide, antimony trioxide, sodium antimonate or zinc borate.

The solid microparticle material may be melt-mixed with the nanocomposite, for example, in a twin-screw extruder or Buss kneader. If many particulate materials are added, it may increase the viscosity, but it may be added at the same time as sepiolite-type clay, and care should be taken not to increase the viscosity too high.

With the exception of sepiolite-type clay, solid particulate material may be present in 0 to about 60 weight percent of the total composition.

(Polymer strengthening agent) Improving the impact strength or toughness of polyamide resins has long been of interest. Resistance to impact crushing or brittle fracture of polyamide moldings is a desirable feature of any molding. Any tendency to break at impact (rather than ductile wind), even brittle, significantly limits the usefulness of such goods. Fractures in ductile materials are further characterized by fractures in large volumes of adjacent materials that yield at the edges of the cracks or by tears rather than sharp, clean fractures with little molecular displacement. A resin with good ductility resists crack propagation caused by impact.

Therefore, any preferred raw material in the compositions of the present invention is a polymer strengthening agent. One type of polymer toughening agent is a functional group that can react with a polyamide (and possibly other polymers present) to produce a composite polyphase resin with improved impact strength against an unreinforced polyamide. Bound polymers, but typically elastomers. Some functional groups that can react with polyamide are carboxyl groups (-COOH), metal neutralized carboxyl groups, amine groups, anhydride groups, epoxy groups, and bromine groups. Since polyamides usually have a carboxyl group (-COOH) and an amine group present, these functional groups can usually react with the carboxyl group and / or the amine group. Such functional groups are usually polymer strengthening agents by grafting small molecules onto existing polymers or by copolymerizing monomers containing the desired functional groups when the polymer strengthening agent molecules are produced by copolymerization. Is "combined" with. As an example of grafting, maleic anhydride may be grafted onto a hydrocarbon rubber using a free radical grafting technique. The resulting grafted polymer has a carboxylic acid anhydride and / or a carboxyl group attached to it.

Various additives have been added to the polyamide resin to improve strength and ductility. For example, the US Patent Gazette (Patent Document 17), issued November 13, 1979, granted to Epstein, incorporated herein by reference, is selected to adhere to polyamide. The improvement of impact strength and ductility by adding a random copolymer is described. In the US Patent Gazette (Patent Document 18) issued on May 12, 1990, incorporated herein by reference, Epstein is a type of polymer toughening agent for polyamides that adheres to polyamides. Sites that promote (graft sites) are preferably present as metal neutralizing carboxyls, adjacent carboxyls (ie, carboxylic acid monomer units flanking metal neutralizing carboxyl monomer units), anhydrides, or epoxy functional groups. Deaf teaches that other functional sites such as sulfonic acids or amines may be effective. These sites will be present in an amount that provides the required grafting.

Preferred polymer tougheners are copolymers of ethylene, propylene and 1,4-hexadiene and, in some cases, norbornadien, said copolymers having 1 to 1 alkyl groups of fumaric acid, maleic acid, maleic anhydride and esters. An unsaturated monomer taken from the class consisting of the monoalkyl ester of the acid having three carbon atoms is grafted onto it. For example, one such polymer is TRX301, available from the Dow Chemical Company (Midland, Michigan, USA).

Another type of polymer strengthening agent is an ionomer containing certain types of ionic groups. The term "ionomer", as used herein, means a polymer in which an inorganic base is attached to a polymer chain ((Non-Patent Document 3)). Ionomers, which act as polyamide enhancers, do not necessarily react with polyamides, but with their ionic groups provided by the solubility of ions (eg, lithium, zinc, magnesium, and manganese ions) in the polyamide melt. It contains an ionic group that becomes stronger due to its compatibility with polyamide. A preferred polymer toughening agent of this type is the formula RCH = CH₂Units derived from alpha-olefins (where R is H or an alkyl having 1-8 carbon atoms) and 0.2 derived from alpha, beta-ethylene unsaturated mono- or dicarboxylic acids. An ionomer with a unit of ~ 25 mol%, in which at least 10% of the acid groups in the unit are neutralized with metal ions having valences in the range 1-3 including both ends. Preferably, the ionomer is Li⁺, Zn⁺², Mg⁺²And / or Mn⁺²It would be a copolymer of ethylene and acrylic acid or methacrylic acid neutralized at least 10% with metal ions such as. For example, one such polymer is DuPont.^TMSurlyn® (patent applicant of the present application).

In addition to the polymer strengtheners described above, two halogenated elastomers, namely isobutylene halogenated-isoprene copolymers and poly brominated (isobutylene-co-4-methylstyrene), are effective strengtheners for polyamides. Has been identified. The latter is commercially available as an Exxpro specialty elastomer from Exxon Mobil Chemical (Houston, Texas, USA). It is considered that it binds to polyamide by the reaction of its benzylic bromine with a polyamide amine terminal group or an amide group [(Non-Patent Document 4)].

In one embodiment there is about 2 to about 30 weight percent of the total composition in the composition, in another embodiment about 5 to about 25 weight percent, and in another embodiment about 8 to about 20 weight percent of the polymer toughening agent. Exists.

The polymer strengthening agent may contain a mixture of two or more polymers, at least one of which must contain a reactive functional or ionic group as described above. Others may or may not contain such functional or ionic groups. For example, preferred polymer toughening agents for use in the compositions described herein are ethylene / propylene / hexadiene ternary copolymers grafted with maleic anhydride and Engage® 8180, Contains a mixture with plastomer polyethylene, such as ethylene / 1-octene copolymer, available from Dow Chemical Company (Midland, Michigan, USA).

(Additive) Other raw materials, particularly those commonly used for thermoplastics, may optionally be added to the composition in amounts commonly used for thermoplastics. Such materials include antioxidants, antistatic additives, heat stabilizers, lubricants, mold release agents, (paint) adhesion promoters, other types of polymers (for forming polymer blends) and the like. Preferably the sum of all these ingredients is less than about 60 weight percent of the composition, more preferably less than about 40, and particularly preferably less than about 25 weight percent.

(Melting and mixing) The compositions described herein can be produced by typical melt mixing techniques. For example, the raw material may be added to a single-screw or twin-screw extruder or kneader and mixed in the usual way. After the materials are mixed, they may be molded (cut) into pellets or other particles suitable for feeding to the melt forming machine. The melt formation can be carried out by conventional methods for thermoplastics, such as injection molding, thermoforming, or extrusion, or any combination of these methods. Some of the raw materials such as fillers, plasticizers, and lubricants (release agents) reduce the wear of solids such as fillers and / or improve dispersion, and / or relatively heat-labile raw materials. It may be added at one or more downstream points of the extruder to reduce the thermal history and / or the loss due to evaporation of the volatile feedstock.

Sepiolite-type clay may be directly melt-mixed with other raw materials at its desired final concentration. Alternatively, a masterbatch containing a relatively high concentration (eg, 20-30% by weight in selected polyamide) of sepiolite-type clay may be prepared by melt mixing, followed by a masterbatch in turn with additional feedstock. Melt and mix to achieve the final composition.

"Melting and mixing" or, more precisely, applying shear stress to the melt of polyamide / sepiolite clay nanocomposites sometimes results in a better dispersion of nanoparticles in the already formed nanocomposites. It will be noticed again. Therefore, the post-treatment of the initially formed nanocomposite by shearing the melt is a preferred process. This can be a process that is easily devoted to improving the dispersion, or more preferably another, such as the polyamide composite mixing with other materials and / or melting and forming the nanocomposite composition. It can occur when liquefied for a reason and then sheared. Types of equipment useful for this purpose include single-screw and twin-screw extruders as well as kneaders.

It was also found that the mixing strength [eg, as measured at extruder speed (rpm per second, rpm)] may affect the properties of the composition, especially toughness. Relatively higher rpm is preferred, but toughness may decrease at mixer rotor speeds that are too high. The optimum mixing intensity depends on the configuration of the mixer, the temperature, the composition during mixing, etc., and is easily determined by a simple experiment.

It should be understood that any preferred raw material and / or amount of raw material may be combined herein with any other preferred raw material and / or amount of raw material.

The component containing the composition heats the composition above the melting point of the polyamide (or the glass transition temperature if the polyamide is amorphous) (and thus liquefies the polyamide), then lowers them below the melting point. It may be produced by cooling to solidify the composition to form a shaped part. Preferably, the part is cooled to at least 50 ° C below the melting point, more preferably at least 100 ° C below the melting point. Most commonly, the composition will ultimately be cooled to ambient temperature, most typically 15-45 ° C.

Articles containing the nanocomposite compositions produced by the present invention can be any method known in the art, such as, but not limited to, injection molding, melt spinning, extrusion, blow molding, thermoforming, or film blowing. May be manufactured by.

The nanocomposite compositions described herein do not significantly adversely affect other properties such as melt viscosity and impact strength, especially when the concentration of clay in the nanocomposite composition is relatively low. Enhances properties such as tensile strength and modulus, flexural modulus and modulus, and thermal deformation temperature properties.

Surprisingly, the reinforced polyamide / sepiolite clay nanocomposites can also demonstrate an increase in elastic energy capacity (Figure 3). As used herein, "elastic energy capacity" means the ability of a material to absorb energy when it is elastically deformed and then recover this energy upon unloading. It is represented by the area below the curve in the elastic region in the stress-strain diagram. Formally, Coefficient of elastic energy capacity = 0.5 * Modulus²/ Elastic strain As a result, articles containing such reinforced nanocomposite compositions should exhibit increased impact resistance, i.e., moderate impact or excellent damping of impact loads.

(Use) Application areas for nanocomposites described herein include, but are not limited to, components in automotive, electrical / electronic, consumer products, and industrial applications. The nanocomposites described herein containing semi-aromatic polyamides are particularly useful for automotive parts that will be exposed to high temperatures, such as underhood automotive applications and high temperature electrical / electronic applications.

In the automotive field, the nanocomposites described herein are used in underhood applications (eg, radiator end tanks, connectors, intake manifolds, air intake resonators, front end modules, engine cooling water outlets, fuel rails). , Ignition coil, engine cover), internal applications (eg switches, handles, seat belt components, airbag containers, pedals, pedal boxes, seat systems), and external applications (eg wheel covers, sunroofs) Can be used for enclosures, door handles, fuel filler flaps).

In the electrical / electronics field, the nanocomposites described herein are connectors, windings, motor armature insulators, light housings, plugs, switches, switch gears, housings, relays, circuit breaker components, terminals. It can be used in applications such as boards, printed circuit boards, and housings for electronic devices.

In the consumer goods sector, the nanocomposites described herein are for power tool housings, sporting goods (eg, ski boots, ski bindings, ice skates, roller skates, tennis rackets), lighters, kitchenware, telephones. Use in applications such as jacks, small appliances (eg steam irons and needles), large appliances (eg oven fans and glass holders), furniture (eg chair bases and arms), eyeglass frames, and packaging films. Can be done.

In the industrial field, the nanocomposites described herein include gears, pulleys, bearings and bearing cages, valves, stadium seats, slide rails for conveyors, casters, HVAC boiler manifolds and conversion valves, as well. It can be used for applications such as pump housings.

The present invention will be further clarified in the following examples. Although these examples represent preferred embodiments of the invention, it should be understood that they are given for purposes of illustration only.

The abbreviations have the following meanings: "cm" means centimeters, "min" means minutes, "g" means grams, "mg" means milligrams, "ksi" "" Means milligrams per square inch, "wt%" means weight percent (percentage), "T"_g"" Means the glass transition temperature, "T_hc"" Means the temperature of crystallization when cooled from the melt, "T"_m"" Means melting point, "M" means mole, "M"_n"" Means number average molecular weight, "PDI" means polydispersity index, M_nEqual to the weight average molecular weight divided by, "MPa" means megapascal, "DSC" means differential scanning calorimetry, "TEM" means transmission electron microscopy, "HDT" means thermal deformation It means temperature, and "rpm" means rotation speed per second.

(Glossary of raw material terms) Aluminum stearate and lubricants were purchased from Chemtura Corporation (Chemtura Corporation (199 Benson Rd, Middlebury, CT 06749), 06749, Connecticut, Middlebury, 199 Benson Road).

Attapulgusite 420-P and 601-P are attapalgyite minerals purchased from Zemex Industrial Minerals Company (Attapulgus, GA 39815, USA), Georgia, USA (39815, USA).

The Engage® Polyolefin Elastomer was provided by the patent applicant of the present application and is currently manufactured by Dow Chemical Company (Midland, Michigan, USA). Engage® 8180 is an ethylene / 1-octene copolymer of 42 wt% comonomer.

HS7.1.1S, heat stabilizer from Shepherd Chemical Co. (Shepherd Norwood, 4900 Beech Street, Norwood, Ohio 45212) I bought it. Irganox® 1010, an antioxidant purchased from Ciba Specialty Chemicals (Tarrytown, NY, USA).

Licowax® PED521 is a polyethylene oxide wax used as a mold release agent available from Clariant Corp. (Charlotte, NC 28205, USA), Clariant Corp. (Charlotte, NC 28205, USA). Is. It has been reported to have an acid value of about 18 mg KOH / g wax.

The M10 52 talc was purchased from Minerals Technologies Inc. (New York, NY, USA).

Pangel® S-9, Pansil®, and Pangel® HV Sepiolite are EM Sullivan Associates, Inc. (Paoli, PA). , USA), purchased from a distributor of manufacturer Torsa (Madrid 28001, PA). Pangel® HV is an ultra-finely ground, unmodified surfaced rheology additive grade sepiolite. S-9 is a leology additive grade sepiolite with an unmodified surface, ultra-finely ground similar to Pangel® HV, but processed in the second grinding step. (Registered Trademark) is a brand of sepiolite that has an unmodified surface and has been ground by a dry grinding method.

Pelestat® 6500, a sodium-containing antistatic polyether esteramide rubber, is Pelestat (1285 Avenues of Americas, New York, NY 10019). I bought it from.

Sodium montmorillonite was purchased from Paikong (Taiwan).

The ethylene / propylene / hexadiene ternary copolymer grafted with TRX301, 2.1% maleic anhydride was purchased from Dow Chemical (Midland, Michigan, USA).

Three types of polyamides have been provided by the patent applicants of the present application: Polyamide A is a copolyamide of terephthalic acid, hexamethylenediamine, and 2-methyl-pentamethylenediamine in which the two diamines are used in a 1: 1 molar ratio. Polyamide B is a copolyamide made from terephthalic acid, adipic acid, and hexamethylenediamine and having a melting point of about 315 ° C. Zytel® 101 is an unreinforced polyamide 6,6.

(Test method) Molecular weight measurement. Viscotek Corporation (Houston, TX) Model T-60ATM Dual Detector Module with Waters 410TM Refractometer Detector (DRI) and Fixed Right Angle Light Scattering and Differential Capillary Viscometer Detector A size exclusion chromatography system consisting of the Model Alliance 2690TM from Waters Corporation (Milford, MA) was used for molecular weight characterization. .. The mobile phase was 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) with 0.01 M sodium trifluoroacetate. dn / dc was measured for the polymer and it was assumed that all of the samples were completely eluted during the measurement.

Tensile modulus, strength and elongation were measured at an elongation rate of 5.08 cm (2 inches) per minute using ASTM (American Society for Testing and Materials) method D256. This method was also used to obtain the stress-strain curve in Figure 3.

The flexural modulus (3 points) was measured using ASTM method D790.

The heat distortion temperature (also known as "heat deflection temperature", "deflection temperature under load", or DTUL) was measured using ASTM method E2092-03.

Notched and unnotched Izod pendulum impact strengths were measured according to ASTM D256-06.

Transition temperature. Melting point T_mWas measured at a heating rate of 10 ° C / min according to ASTM D3418-82. The peak of endothermic melt was taken as the melting point. Crystallization temperature T_hcWas taken as the peak of crystallization heat generation during cooling from the melt. Glass transition temperature T_gWas taken as an inflection point of heat capacity during the second heating cycle.

(Mixing and molding method) All polyamide resins were dried at 90 ° C for 12 hours before extrusion and molding. Mineral additives were used as received unless otherwise stated.

Formulation Method A The polymer composition was prepared by blending with a 30 mm Werner and Pfleiderer twin screw extruder. Panger® S-9 and other minerals were side-fed to barrel 5 (10 barrels), and all plasticizers were added using a liquid injection pump. The raw materials were mixed and added through the rear feed port (barrel 1) of the extruder. Any exceptions to this method are noted in the examples. The barrel temperature was set at 340 ° C, which resulted in a melting temperature of 290-350 ° C depending on the composition as well as the extruder speed and screw rpm.

Formulation Method B The polymer composition was prepared by blending in a 30 mm bath co-kneader (Buss Co Kneader). The base resin (polyamide A or polyamide B) was added through the rear feed port (barrel 1) of the extruder and Pangel® S-9 sepiolite was added to the second feed port. Any exceptions to this method are noted in the examples. The barrel temperature was set at 340 ° C, which resulted in a melting temperature of 290-350 ° C depending on the composition as well as the extruder speed and screw rpm.

Formulation Method The C polymer composition was prepared by blending with a 30 mm Warner and Pfriedler twin screw extruder. Panger® S-9 sepiolite and other minerals were mixed and added through the rear feed port (barrel 1) of the extruder, except that they were laterally fed into barrel 5 (10 barrels). It was. Any exceptions to this method are noted in the examples. The barrel temperature was set at 290 ° C, which resulted in a melting temperature of 290-300 ° C depending on the composition as well as the extruder speed and screw rpm.

Molding method. The resin was molded into an ASTM test specimen on an Arburg 1.5 oz (43 g) or Nissei 6 ounce (170 g) injection molding machine. The melting temperature for Zytel® 101 (polyamide 6,6) was 290 ° C and the mold temperature was 70-80 ° C. The melting temperature for polyamide A and polyamide B was 310 ° C, and the mold temperature was 140 ° C unless otherwise stated.

(Example 1) (Preparation of polyamide A / sepiolite nanocomposite masterbatch using twin-screw extruder) A masterbatch of polyamide A containing 20% by weight Pangel® S-9 sepiolite was prepared using blending method A. SEC characterization is Polymer M_nIs 11370, suggesting that PDI = 3.54. TEM analysis suggested that the masterbatch would form a suitable nanocomposite. Sepiolite nanoparticles were well dispersed with some larger aggregates still present (Fig. 2). Not only the test sample of the polyamide A-based resin as a control, but also the test sample was molded as described above. Table 2 shows the results of HDT and flexural modulus.

(Example 2) (Preparation of polyamide B / sepiolite nanocomposite masterbatch using twin screw extruder) A masterbatch sample of polyamide B containing 20% by weight Pangel® S-9 sepiolite was prepared using Formulation Method A. SEC characterization of extruded polymer M_nIs 20990, suggesting that PDI = 2.04. The test sample was molded as described above. Table 2 shows the results of HDT and flexural modulus.

(Example 3) (Preparation of polyamide A / sepiolite nanocomposite masterbatch using bath co-kneader) 14.3 A masterbatch sample of polyamide A with weight% Pangel® S-9 sepiolite was prepared using blending method B. SEC characterization is Polymer M_nIs 11370, suggesting that PDI = 3.54. TEM analysis suggested that the particles were well dispersed and some larger aggregates were still present, allowing the masterbatch to form suitable nanocomposites.

(Example 4) (Preparation of polyamide A / 3 wt% sepiolite nanocomposite) A sample of the masterbatch (20 wt% S-9 sepiolite in polyamide A) prepared in Example 1 was combined with additional polyamide A (15 wt% masterbatch, 85 wt% polyamide A) using formulation method A. An extruded nanocomposite containing 3 wt% sepiolite was prepared. The results of thermal analysis are shown in Table 1. The resulting nanocomposite crystallized at a higher temperature (277 ° C) when cooled from the melt than the polyamide A control (255 ° C), suggesting that sepiolite is an effective nucleating agent for polyamide A. The test sample was molded as described above. Table 2 shows the results of HDT and flexural modulus.

(Example 5) (Preparation of polyamide B / 3 wt% sepiolite nanocomposite) A sample of the masterbatch (20 wt% S-9 sepiolite in polyamide B) prepared in Example 2 was combined with additional polyamide B (15 wt% masterbatch, 85 wt% polyamide B) using Formulation Method A. An extruded nanocomposite containing 3 wt% sepiolite was prepared. The results of thermal analysis are shown in Table 1. The test sample was molded as described above. Table 2 shows the results of HDT and flexural modulus.

(Example 6) (Preparation of polyamide B / 1 wt% sepiolite nanocomposite) A sample of the masterbatch (20 wt% S-9 sepiolite in polyamide B) prepared in Example 2 was combined with additional polyamide B (5 wt% masterbatch, 95 wt% polyamide B) using Formulation Method A. An extruded nanocomposite containing 3 wt% sepiolite was prepared. The results of thermal analysis are shown in Table 1. The test sample was molded as described above. Table 2 shows the results of HDT and flexural modulus.

(Example 7) (Preparation of polyamide A / 1 wt% sepiolite nanocomposite) A sample of the masterbatch (20 wt% S-9 sepiolite in polyamide A) prepared in Example 2 was combined with additional polyamide B (5 wt% masterbatch, 95 wt% polyamide A) using compounding method A. An extruded nanocomposite containing 1 wt% sepiolite was prepared. The results of thermal analysis are shown in Table 1. The test sample was molded as described above. Table 2 shows the results of HDT and flexural modulus.

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(Example 8, Comparative Example A) (Preparation and properties of reinforced semi-aromatic polyamide nanocomposites) Two fortified semi-aromatic polyamide materials were prepared with the compositions shown in Table 3. They were prepared using Formulation Method A, except that the masterbatch prepared in Example 1 was added at the rear feed port in Example 8. Test specimens were molded as described above, except that Perestat® 6500 was added to the compound pellet prior to injection molding. The results shown in Table 3 demonstrate increased stiffness and strength of the nanocomposite compared to controls (Comparative Example A) with minimal impact on unnotched Izod impact strength.

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(Examples 9 to 11, Comparative Example B) (Preparation and properties of aliphatic polyamide nanocomposites) A nanocomposite masterbatch of Zytel® 101 Polyamide 6,6 and 20 wt% S-9 Sepiolite was prepared using Formulation Method C. This nanocomposite masterbatch (Example 9) was then used to contain 3% by weight (Example 10) and 1% by weight (Example 11) sepiolite-containing Zytel® 101 / sepiolite nanocomposite. The material was prepared. Test specimens of three nanocomposites and Zytel® 101-based resins were molded as described above. Examples 10 and 11 demonstrate improvements in tensile modulus, tensile strength, flexural modulus, and heat deflection temperature in nanocomposites compared to Comparative Example B.

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(Examples 12 to 15, Comparative Example C) (Preparation and properties of reinforced aliphatic polyamide nanocomposites) Reinforced Zytel® 101 Nanocomposite Resin Containing 1, 2, 3 and 5 wt% S-9 Sepiolite Using Formulation Method C Using the Nanocomposite Masterbatch Prepared in Example 9. Was prepared. The composition is shown in Table 5. A control test sample containing no four nanocomposites and no sepiolite was molded as described above. Examples 12-15 emphasize that the addition of a small amount of sepiolite achieved significant improvements in tensile and flexural modulus, tensile strength, and HDT compared to Comparative Example C.

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The stress-strain curves obtained during standard tensile measurements show that in addition to the improved stiffness and strength provided by the addition of sepiolite to the reinforced polyamide matrix, the elastic energy capacity of Example 14 nanocomposites is also controlled ( It was shown to be improved by 45% compared to Comparative Example C) (Fig. 3).

(Examples 16 to 20; Comparative Example D) (Comparison of Rheology Additive Grade Sepiolite Pangel S-9 with Other Mineral Additives) Attapulsite 420-P is a high quality attapulsite treated to provide viscosity retention for a variety of applications, including both aqueous and solvent based systems. Attapulsite 601-P is described as the finest grade attapulsite that gels available clay. It is a special size and is processed to thicken industrial products such as paints, plastic coatings, flexographic inks, and adhesives. Pangel® HV is a rheological additive for aqueous systems prepared from very pure sepiolite. Pancil® is a refined version of sepiolite designed for absorption applications such as cat sand boxes. Pangel® S-9 and Pangel® HV are both rheological additive grade sepiolites, and Pancil® is not.

Samples were prepared using Formulation Method A, except that a micron-sized mineral additive was added behind the extruder along with the resin. All samples were prepared using 97% Polyamide A and 3% by weight of the specified mineral additives. The sample was molded at a mold temperature of 115 ° C with a melting temperature of 310 ° C.

Table 6 shows the thermal deformation temperature. Example 17 contained ground and ultrafine grade sepiolite and showed a dramatically increased HDT compared to the other examples. In addition, all of the examples showed a significant improvement in HDT compared to Comparative Example D.

<tables num="1"><img id="000007" he="62" wi="106" file="JP5337692B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><u style="single"> The main inventions described in the present specification are listed below.</u><u style="single">1.</u><u style="single"> a. With at least one thermoplastic polyamide,</u><u style="single"> b. Unmodified sepiolite-type clay nanoparticles with particle widths and thicknesses of less than 50 nm, respectively.</u><u style="single"> A nanocomposite composition comprising.</u><u style="single">2.</u><u style="single"> The composition according to 1. above, wherein the nanoparticles are present in an amount of about 0.1 to about 30% by weight based on the combined weight of the polyamide and the nanoparticles.</u><u style="single">3.</u><u style="single"> The composition according to 2. above, wherein the unmodified sepiolite-type clay is present in an amount of about 0.1 to about 4% by weight based on the combined weight of the polyamide and the unmodified sepiolite-type clay.</u><u style="single">4.</u><u style="single"> The composition according to 1. above, wherein the sepiolite-type clay nanoparticles are of the rheology additive grade.</u><u style="single">5.</u><u style="single"> The composition according to 1. above, wherein at least one of the polyamides is an aliphatic polyamide or a semi-aromatic polyamide.</u><u style="single">6.</u><u style="single"> The aliphatic polyamides are polytetramethylene adipamide, polyhexamethylene adipamide, polyhexamethylene azelaamide, polyhexamethylene sebacamide, polyhexamethylene dodecanoamide, and bis (para-aminocyclohexyl) methandodecano. It is characterized by being selected from amides, polycaprolactams, poly-11-amino-undecanoic acids, copolymers consisting of the above polymers or their components, and / or terpolymers consisting of the above polymers or their components. The composition according to 5. above.</u><u style="single">7.</u><u style="single"> The semi-aromatic polyamide is partially derived from a monomer containing a divalent aromatic group, one or more homopolymers, copolymers, terpolymers, and more multidimensional polymers, and one or more kinds of polymers. It is characterized by being selected from blends of aliphatic polyamides with one or more homopolymers, copolymers, terpolymers, or more multidimensional polymers derived in part from monomers containing divalent aromatic groups. The composition according to 5. above.</u><u style="single">8.</u><u style="single"> The semi-aromatic polyamide is poly (m-xylylene adipamide), hexamethylene adipamide / hexamethylene terephthalamide copolyamide; hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide copolyamide; poly ( Dodecamethylene terephthalamide); Poly (decamethylene terephthalamide); Decamethylene terephthalamide / decamethylene dodecanoamide / copolyamide; Poly (nonamethylene terephthalamide); Hexamethylene isophthalamide and hexamethylene adipamide polyamide; Hexa The composition according to 5. above, which is selected from a polyamide of methylene terephthalamide, hexamethylene isophthalamide, and hexamethylene adipamide; and a copolymer or mixture of these polymers.</u><u style="single">9.</u><u style="single"> The composition according to 1. above, further comprising a polymer strengthening agent present in an amount of about 2 to about 30% by weight based on the total composition.</u><u style="single">10.</u><u style="single"> 9. The composition according to 9. above, wherein the polymer strengthening agent contains a carboxyl group, an anhydride group, an amine group, an epoxy group, a halogen group, and a functional group selected from a mixture thereof.</u><u style="single">11.</u><u style="single"> The polymer strengthening agent has the formula RCH = CH</u>_{<u style="single">2</u>}<u style="single">Units derived from alpha-olefins (in the formula, R is an alkyl having H or 1-8 carbon atoms) and 0.2 ~ derived from alpha, beta-ethylene unsaturated mono- or dicarboxylic acids. It is an ionomer with a unit of 25 mol%, characterized in that at least 10% of the acid groups of the unit are neutralized with metal ions having a valence in the range of 1 to 3 including both ends. The composition according to 9. above.</u><u style="single">12.</u><u style="single"> Based on the sum of all the raw materials in the composition, it further contains about 0.1 to about 50% by weight of the reinforcing agent, which is kaolin clay, talc, wollastonite, mica, and carbon dioxide, except for sepiolite type clay. Calcium; various forms of glass such as fibers, ground glass, non-hollow or hollow spheres; carbon black or carbon as carbon fibers; titanium dioxide; aramids in the form of short fibers, fibrils or fibrils; and two or more of these The composition according to 1. above, which is selected from a mixture of.</u><u style="single">13.</u><u style="single"> a. Approximately 0.1-4% by weight of unmodified sepiolite-type clay nanoparticles,</u><u style="single"> b. Polyamide 6,6; Polyamide 6; Copolyamides of terephthalic acid, hexamethylenediamine, and 2-methyl-pentamethylenediamine; at least selected from copolyamides made from terephthalic acid, adipic acid, and hexamethylenediamine. With one kind of polyamide</u><u style="single"> c.0 to about 20% by weight polymer strengthening agent</u><u style="single"> i. Ethylene / propylene / hexadiene copolymer grafted with maleic anhydride, and</u><u style="single"> ii. Copolymers of ethylene with acrylic acid or methacrylic acid, which are at least 10% neutralized with metal ions,</u><u style="single"> With polymer fortifiers containing at least one of</u><u style="single"> The nanocomposite composition according to 1. above, which comprises.</u><u style="single">14.</u><u style="single"> A product comprising the composition according to 1. above.</u><u style="single">15.</u><u style="single"> The article according to 14. above, which is an automobile component.</u><u style="single">16.</u><u style="single"> The automobile components are radiator end tanks, intake manifolds, air intake resonators, front end modules, engine cooling water outlets, fuel rails, ignition coils, engine covers, switches, handles, seatbelt components, airbag containers. The article according to 15. above, characterized in that it is selected from pedals, pedal boxes, seat systems, wheel covers, sunroof enclosures, door handles, and fuel filler flaps.</u><u style="single">17.</u><u style="single"> Choose from connectors, windings, motor armature insulators, light housings, plugs, switches, switch gears, housings, relays, circuit breaker components, terminal boards, printed circuit boards, and housings for electronics. The article according to 15. above.</u><u style="single">18.</u><u style="single"> Power tool housings, sporting goods, lighters, kitchen utensils, telephone jacks, small appliances, large appliances, furniture, eyeglass frames, packaging films, gears, pulleys, bearings, bearing cages, valves, stadium seats, The article according to 15. above, characterized in that it is selected from slide rails for conveyors, casters, HVAC boiler manifolds, conversion valves, and pump housings.</u><u style="single">19.</u><u style="single"> The article according to 18. above, wherein the sporting goods are selected from ski boots, ski bindings, ice skates, roller skates, and tennis rackets.</u>

<figref num="1">It is a schematic of the dimension of sepiolite type clay fiber.</figref><figref num="2">FIG. 5 is a transmission electron micrograph of a polyamide A / sepiolite nanocomposite masterbatch prepared using a twin-screw extruder containing 20% by weight sepiolite (Panger® S-9).</figref><figref num="3">Draw stress vs. strain curves for reinforced polyamide resins with sepiolite (Panger® S-9) with (Example 14) and without (Comparative Example C).</figref>