MXPA98005655A - Rigid article thermoplastic with cover your - Google Patents

Abstract

The present invention provides a process for making articles of manufacture, as well as the articles themselves comprising thermoplastic nylon materials and thermoplastic polyurethane blends capable of adhering to thermoplastic nylon materials, wherein the thermoplastic polyurethane blends comprise: a) 3 a 200 parts of a styrene / alpha-methylstyrene / acrylonitrile / alkyl acrylate terpolymer of 1 to 6 carbon atoms with a glass transition temperature (Tg) below 0 ° C; b) 100 parts of a thermoplastic polyurethane produced of a diisocyanate, a diol of 2 to 10 carbon atoms and a polyether and / or polyol based on polyester; and c) 0 to 50 parts of various additives including lubricants, pigments, stabilizers, etc. The manufacturing items can be configured as power tool housings, luggage handles, gear shifts, automobile pedals, and

Description

RIGID ARTICLE THERMOPLASTIC WITH SOFT COVER 1. Field of the Invention The present invention relates to articles of compounds that include materials that are self-adhesive with a particular class of thermoplastic elastomers comprising thermoplastic polyurethanes. 2. Background of the Invention Rigid thermoplastics such as ABS, nylon 6 filled with glass, and polycarbonate are used for a variety of engineering and / or structural applications such as housings for power tools, luggage handles, travel gears, automobile pedals, etc.; for many of these applications there is a need to cover or bond these articles with a soft elastomer layer. This layer serves to provide a comfortable ergonomic feel, reduced detachment and increased resistance to abrasion.

Ideally, this combination of "hard" and "soft" materials is produced through a thermoforming operation such as co-injection molding, multi-layer extrusion or blow molding.

The U.S. Patent No. 5,154,979 addresses a molded article and a method for making these articles. The article consists of a base made of a first thermoplastic polymer. A joint made of a second thermoplastic polymer melts on top of the base. One or both first or second polymer should contain 5 to 75 percent by weight, based on the mixture, of an olefin homopolymer and / or copolymer. Typical examples would include an engineering thermoplastic power tool with a hand grip made of an elastomer such as TPU, Santoprene or the like. Unfortunately, the article disclosed in the '969 patent provides insufficient abrasion resistance in the elastomeric portion, as well as being too hard for most uses that would require an elastomeric coating.

So far most of the thermoplastic elastomers with the required softness (Shore A < 80) that are useful as a soft shell, including polymers of EPDM based on propylene and ethylene, styrene block ter or copolymers or plasticized PVC they had insufficient adhesion to the rigid thermoplastic substrate, unless they were fixed using separate adhesives or mechanical interlaces. Unfortunately, these soft TPEs also have insufficient resistance to engineering applications. Although they have the desired Shore hardness, good adhesion and abrasion resistance, plasticized TPU / TOPU mixed with phthalate esters such as DOP) are not acceptable due to the tendency of the plasticizer to migrate in the thermoplastic substrate and cause stress cracks or to migrate at the TPU / thermoplastic interface, as to weakening adhesion. 3. Compendium of the Invention The present invention provides a process for making articles of manufacture as well as the articles themselves comprising thermoplastic nylon materials and thermoplastic polyurethane blends capable of adhering to thermoplastic nylon materials, wherein the thermoplastic polyurethane blends comprise: a) 3 a 200 parts of a styrene / alpha-methylstyrene terpolymer (acrylonitrile / Cl-Cß of alkyl acrylate with a glass transition temperature / Tg) below 0 ° C; b) 100 parts of the thermoplastic polyurethane produced from a diisocyanate, a C2-C10 diol, and a polyol based on polyether and / or polyester, and; c) 1 0 to 50 parts of various additives, including lubricants, pigments, stabilizers, etc.

The articles of manufacture can be configured as accommodation for power tools, luggage handles, displacement gears, automobile pedals, etc. 4. Description of the Preferred Modalities The article of the present invention is a combination of a rigid engineering thermoplastic, namely, nylon, covered with a special TPU composite having a Shore A hardness < 90. This combination shows excellent adhesion and abrasion resistance and is easily produced by conventional thermoforming operations without the use of adhesive or mechanical interlayers.

The special TPU compound is based on: a) 3 to 200 parts of a styrene / alpha-methylstyrene / acrylonitrile / alkyl acrylate terpolymer of Cl-Cß with a glass transition temperature / Tg) below 0 ° C; b) 100 parts of the thermoplastic polyurethane produced from a diisocyanate, a C2-C10 diol, and a polyether based polyether and / or polyester, and; c) 0 to 50 parts of various additives including lubricants, pigments, stabilizers, etc.

The resulting composition has a Shore A hardness < 90. The relative hardness of elastic materials such as rubber or soft plastics can be determined with an instrument called a Shore A durometer. If the sensor fully penetrates the sample, a reading of 0 is obtained, and if penetration does not occur, it results a reading of 100. The reading is unlimited. Materials previously combined together in a melt process preferably use a twin screw extruder.

Optionally, one or more UV stabilizers, one or more compatibilizers and one or more additives that are selected from the group consisting of lubricants and inhibitors, stabilizers against hydrolysis, thermal stabilizers, flame retardants, dyes, pigments, organic fillers and / or inorganic and reinforcing agents can be added to the composition.

The TPUs that can be used according to the present invention can be prepared by the reaction of: a) organic diisocyanates, preferably aromatic, in particular 4, 4 '- diphenylmethane diisocyanates, with b) polyhydroxy compounds, preferably substantially linear polyhydroxy compounds, having molecular weights of 500 to 8000 m, in particular of glycol polyadipates of polyalkylene having from 2 to 6 carbon atoms in the alkylene moiety and molecular weights from 500 to 6000 or from polyetherahydrofuran containing hydroxyl with a molecular weight of 500 to 8000, and c) diols as chain extenders having molecular weights of 60 to 400, in particular 1,4-butanediol. in the presence of: d) catalysts and optionally e) auxiliaries and / or f) additives at elevated temperatures.

Organic diisocyanates suitable for use in the manufacture of the TPUs of the invention are, for example, the aliphatic, cycloaliphatic diisocyanates, preferably aromatic. Specific examples are: aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 2-methyl-lx 5 -pentamethylene diisocyanate, 2-ethyl-1, 4-butylene diisocyanate and mixtures of when two of the aliphatic diisocyanates, cycloaliphatic diisocyanates such as isophorone diisocyanate, cyclohexane 1,4-diisocyanate, cyclohexane-l-methyl-2,4-diisocyanate and cyclohexane-l-methyl-2,6-diisocyanate and corresponding isomer mixtures and preferably isomeric diisocyantes, 4, 4'-, 2,4'- or 2, 2'-dicyclohexylmethane diisocyanate and the corresponding isomeric mixtures and preferably the aromatic diisocyanates such as toluylene 2,4-diisocyanate, mixtures of 2,4- and 2,6- toluene diisocyanate, 4, 4 '-2, 4'- and 2, 2'-diphenylmethane diisocyanate, mixtures of 2x4' - and 4x4-di-vinyl diisocyanate, urethane modified liquid 4, 4 '-y / o2, 4 '- diphenyl-2,4-diisocyanate-diisocyanate, 1,2-diphenylethane, mixtures of 4,4'-2,4-and 2 , 2'-diisocyanate-1, 2-diphenylethane, preferably those having a content of 4,4'-diisocyanato-1,2-diphenylethane of at least 95% by weight, and 1, 5-naphthalene diisocyanate. Preference is given to the use of the diphenylmethane diisocyanate isomer mixtures having a content of 4,4-diphenyl diisocyanate greater than 96% by weight and in particular 4,4 '- essentially pure diphenyl-diisocyanate.

The polyhydroxy compounds having molecular weights of 500 to 8000 are the polyetherols and in particular the polyesterols. However, it is also possible to use other hydroxy-containing polymers containing ether or ester groups as bridging members, for example polyacetals such as polyoxymethylenes and in particular water-soluble formulas, for example, formal polybutanediol and formal polyhexanediol and polycarbonates, in particular those formed of diphenyl carbonate and 1,6-hexanediol prepared by transesterification. The polyhydroxy compound must be at least predominantly linear, that is to say, dysfunctional within the meaning of the isocyanate reaction. The mentioned polyhydroxy compounds can be used as individual components or in the form of mixtures.

Suitable polyetherols can be prepared from one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene moiety in a conventional manner, for example by anionic polymerization with alkali metal hydroxides, such as sodium hydroxide. or potassium hydroxide, or alkyl metal alcoholates, such as sodium methoxide, sodium ethoxide, potassium ethoxide or potassium isopropoxide, as catalysts and in the presence of at least one molecule of the initiator containing from 2 to , preferably 2 atoms of reactive hydrogen or by the carionic polymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate, etc., or bleaching earths as catalysts.

Preferred alkylene oxides are, for example, tatrahydrofuran, 1,3-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and in particular ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternatively in succession or as mixtures. Suitable initiator molecules are for example; water, organic dicarboxylic acids, such as succinic acid, adipic acid and / or glutaric acid, alkanolamines such as ethanolamine, N-alkylaminolamines, N-alkyldialkanolaraines, for example, N-methyl and N-ethyl-diethanolamine and preferably dihydric alcohols which may contain ether linkages, for example, ethanediol, 1,2-propanedium, 1,3-propanedium, 1,4-butanediol, diethylene glycol, 1,5-entanedium, 1,6-h-hexanediol, glycol of dipropylene, 2-methyl-l, 5-pentanediol and 2-ethyl-l, 4-butanediol. The initiator molecules can be used individually or as mixtures.

Preference is given to the use of polyetherols of 1,2-propylene oxide and ethylene oxide in which more than 50%, preferably 60 to 80%, or OH groups are primary hydroxyl groups and wherein at least Some units of the ethylene oxide are present as terminal blocks. These polyetherols can be obtained, for example, by polymerization in the first initiator molecule of 1,2-propylene oxide and then the ethylene oxide, or first all the 1,2-propylene oxide mixed with some of the ethylene oxide. and then the remainder of the ethylene oxide or step by step first some of the ethylene oxide, then all the 1,2-propylene oxide and then the remaining ethylene oxide. Other preferred possibilities are the hydroxyl-containing polymerization products of tetrahydrofuran.

Essentially linear polyetherols having molecular weights of 500 to 8000 preferably 600 to 6000, in particular 800 to 3500, polyoxytetramethylene glisols preferably having molecular weights of 500 to 2800. They can be used not only individually but also in the way of mixtures with one and the other.

Suitable polyesterols can be prepared, for example, from dicarboxylic acids of 2 to 12, preferably 4 to 6 carbon atoms and polyhydric alcohols. Suitable dicarboxylic acids are for example; aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, acetalic acid and seracic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, for example in the form of a mixture of succinic acid, glutáriso or adipic acid. In order to prepare the polyesterols it could be advantageous to use the corresponding dicarboxylic acid derivatives, such as dicarboxylic or diester monoesters having 1 to 4 carbon atoms in the alcohol moiety, the dicarboxylic anhydrides or decarbonyl dichlorides instead of the dicarboxylic acids. Examples of the polyhydric alcohols are glycols of 1 to 10, preferably 2 to 6 carbon atoms such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1, β-hexanediol. , 1,10-decanediol, 2, -dimethylpro-ano-1,3-diol, 1,3-propanediol and dipropyiene glycol. Depending on the properties desired, the polyhydric alcohols can be used alone and can optionally be mixed with one another.

It is also possible to use carbonic acid esters with the diols mentioned, in particular those having 4 to 6 carbon atoms, such as 1,4-butanedium and / or 1,6-hexanediol, condensation products of hydroxycarboxylic acids , for example, tp-hydroxycaproic acid and preferably the polymerization products of lactones, for example the substituted or unsubstituted w-caproicones.

Preferred polyesterols are the polyadipates of ethanediol, 1,4-polyadipates of butanediol, ethanediol 1 / 1,4-polyadipates of butanediol, 1, β-hexanediol / polyadipates of neopentyl glycol, 1,6-hexanediol 1/1, 4-polyadipates of butanediol and polycaprolactones.

The polyesterols have molecular weights of 500 to 6000, preferably 800 to 3500.

Suitable chain extenders having molecular weights of from 60 to 400, preferably from 60 to 300, are preferably aliphatic diols of 2 to 12 carbon atoms, preferably of 2.4 or 6 carbon atoms, for example, ethanediol , 1, 6-hexanediol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol. However, it is also possible to use diesters of terephthalic acid with glycols of 2 to 4 carbon atoms, for example, the terphthalate of visethylene glycol, 1,4-terephthalate of butanediol and hydroxyalkylene ethers of hydroquinone, for example, 1 -di- (beta-hydroxyethyl) -hydroquinone and also polytetramethylene glycols having molecular weights of 162 to 370.

To establish the hardness index, the formative components can vary within relatively large molar proportions keeping in mind that the hardness is increased with the increased level of the chain extenders.

To prepare the relatively soft TPUs, which are especially preferred for use in the invention, for example those having a Shore A hardness of at least 90, the use of essentially dysfunctional polyhydroxyl compounds (b) and the diols (c) is advantageous. in a molar ratio of 1: 0.1 to 1: 4.5, preferably 1: 0.5 to 1: 4.0, so that the mixtures resulting from (b) and (c) have an equivalent weight of hydroxy greater than 200, in particular from 239 to 450, while it is greater than 200 and in particular from 239 to 450.

Suitable catalysts, in particular the reaction between the reaction of the NCO groups of the diisocyanates (a) and the hydroxyl groups of the formative components (b >) and (c) are the usual tertiary amines, such as triethylamine, dimethycyclohexylamine , N.methylmofoline, N, N-dimethylpiperazine, diazabicium (2.2. -2) octane and the like, in particular organic metal compounds such as ditanic esters, iron compounds, tin compounds, for example, tin diacetate, dioctoate tin, dilaurate tin or dialkyl tin salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate and the like. The catalysts are usually used in amounts of 0.001 to 0.1 parts by weight per 100 parts by weight of the mixture of the polyhydroxy compounds and diols.

In addition to the catalysts, the TPU formative components may also contain auxiliaries and / or additives. Examples are lubricants, inhibitors, stabilizers with hydrolysis, flame retardants, dyes, pigments, inorganic and / or organic fillers and reinforcing agents.

To prepare the TPUs, the formative components, i.e., the diisocyanate compound, polyhydroxy compound and one or more of the chain extenders are made to react in the presence of a catalyst and in the presence or absence of auxiliaries and / or additives in amounts that the equivalent ratio of the NCO groups of diisocyanates to the total number of the hydroxyl groups of the polyhydroxy and the chain extender compounds is from 0.95 to 1.10: 1, preferably 0.98 to 1.08: 1, in particular about 1.0 to 1.05: 1.

The TPUs that can be used in accordance with the present invention and usually contain from 8 to 20% by weight preferably from 8 to 16% by weight based on the total weight of the urethane groups and have a melt flow index to 190 ° C. under 21.6 Kg. from 1 to 500, preferably from 1 to 200, can be prepared by the extruder technique or the belt technique by discontinuous or continuous mixing of the components, the mixture reacting in an extruder or on a 60 ° support belt to the 250 ° C, preferably from 70 ° to 150 ° C, and then the granulation of the resulting TAPU. The technique of the reactor extruder as is well known in the art is the most preferred. It may be advantageous to heat the resulting TPU from 80 ° to 120 ° C, preferably from 100 ° to 110 ° C, for a period of 1 to 24 hours before the next process.

One or more acrylates based on rubbers of the composition, usually comprise a terpolymer. An example of a commercially available illustrative material is Goodyear Chemicals' Sunigum®! One or more UV stabilizers can be used as additives that will be absorbed and dissipate the energy of preference by relieving excited molecules of excess energy and releasing themselves as heat. In general, preferred stabilizers for use herein will be effective in the range of 300 to 360 nm. An example of the suitable UV and the thermal stabilizers are the derivatives of O-hydroxybenzophenone, o-hydrophenylsalicylates, 2, - (0-hydroxyphenyl) -benzotriazoles and interrupted phenols.

It was found that the particular compositions of the UV stabilizer of the claimed invention surprisingly confers the thermal stability without the fogging and yellowing found in many of the stabilized UV compositions of the prior art.

Also what is suitable for use herein as UV stabilizers are the light stabilizers of interrupted amine. Preferred UV stabilizers are those which have sterically interrupted benzotriazole stabilizing active ingredients. It will be appreciated that many of the UV stabilizers are concentrates that contain other materials in addition to the active ingredient. Particularly preferred active ingredients for use as UV stabilizers are 2- (2-hydroxy-3,5-di-tert-amyl-phenyl) -2H-benzotriazole, 1,6-hexanedilbis (3-benzotriazole-N-yl) 4-hydroxy-5-tert-butyl) -propounded phenyl and mixtures thereof.

In particular, one or more of the most preferred UV stabilizers for use in the invention will be the stabilizer concentrates containing the above-mentioned most preferred active ingredients. These stabilizing concentrators will preferably also contain thermoplastic polyurethanes (TPU) and 1,3,5-triglycidyl-isocyanurate. These UV stabilizer concentrates are observed in DE 4211335 A, the information of which is incorporated herein by reference. Most preferred UV stabilizer concentrates will contain about 40 to 80 percent by weight of thermoplastic polyurethanes, 10 to 30 percent by weight 1, 3, 5-triglycylyl-isocyanurate and 10 to 30 percent by weight 2- (2-hydroxy) 3, 5-di-tert-amyl-phenyl) -2H-benzotriazole, 1,6-hexanedylbis (3-benzotriazol-N-yl) -4-hydroxy-5-tert-butyl) phenyl propionate and mixtures of the same.

In addition, the thermoplastic polyurethane compositions of the invention may optionally also contain one or more compatibilizing polymers. These compatibilizing polymers generally comprise copolymers formed from styrene, alpha-methylstyrene, crilonitrile, methacrylonitrile, butadiene, acrylate and mixtures thereof. Preferred compatibilizers are poly (styrene, acrylonitrile) and ABS. Poly (styrene-acrylonitrile) is especially preferred.

Finally, the thermoplastic polyurethane compositions of the invention may optionally also contain additives selected from the group consisting of lubricants, inhibitors, anti-hydrolysis stabilizers, flame retardants, dyes, pigments, organic and / or inorganic fillers, and agents reinforcers. Particularly preferred additives are dyes and pigments. Titanium dioxide is a pigment that is commonly used. Of course those skilled in the art will appreciate that the incorporation of these dyes and pigments depends on the desired appearance of the end-use application.

With respect to the above components of the thermoplastic polyurethane compositions of the invention, these compositions preferably will contain from 50 to 100% of one or more of the thermoplastic polyurethanes, greater than 10 to 49% of one or more acrylate-based rubbers and from 0.1 to 5.0% of active ingredients of one or more UV stabilizers, as based on the combined total weight of the components.

More preferably, the thermoplastic polyurethane compositions of the invention will contain from 60 to 80% of one or more of the thermoplastic polyurethanes, greater than 20 to 40% of one or more acrylate-based rubbers and from 1.0 to 4.0% of the active ingredient. of one or more UV stabilizers, as based on the combined total weight of the components.

If the thermoplastic polyurethane composition of the invention also comprises a compatibilizing polymer, this polymer should be present in an amount of 1 to 10% as based on the total weight of the combined components. More preferably, the thermoplastic polyurethane composition comprising a compatibilizing polymer will contain less than 5% of the polymer and more preferably will comprise from 2 to 4% of the compatibilizing polymer. It will be appreciated that the additives will be present in amounts that depend on the desired final properties of the composition.

It will be appreciated that in the invention, the thermoplastic polyurethane composition is a mixture wherein the predominant matrix comprises thermoplastic polyurethane. The particles of one or more acrylate-based rubbers are dispersed in the matrix. If present, the compatibilizing polymer will serve as the interface between the acrylate-based rubber particles and the TPU matrix. Also interdispersed within the TPU matrix will be the UV stabilizers.

The rigid thermoplastic material of the claimed article comprises nylon. As used herein, the term "nylon" is a generic term for any long chain synthetic polymer amide having recurring amide groups as an integral part of the polymer backbone.

Certain nylons are identified by the number of carbon atoms in the diamine and the dibasic acid that is used to produce them; thus, for example, nylon 6/6 is a polymer produced by the condensation of hexamethylene diamine and adipic acid. Some nylons are produced by the condensation of only one reactive species, and are usually produced from a lactam. This latter class of nylons is generally identified by the number of carbon atoms in the monomer that is used to produce them, thus, for example, poly (aminocripoic acid) is produced by the polymerization of prolactam and is referred to as "nylon". 6".

Examples of the nylons (polyamides) that can be used in the articles and the process of the invention include, without limitation, nylon -6; nylon-6; nylon-6.10: nylon-4.6; nylon-6.12; nylon-11; nylon-12; partially aromatic nylon copolymers such as nylon-6/6, T; nylon-6.6 / 6, 1 / 6T; and so on and mixtures of these. Suitable nylons are available from BASF Corporation, Mount Olive, New Jersey under the trademark Ultramid®. Preferred among these are nylon-6 and nylon -6,. The nylons used in the invention have average molecular weight numbers of preferably at least about 10,000 and more preferably at least about 15,000. The average number of molecular weights of the preferred nylons can be up to about 40,000 and particularly up to about 20,000.

A nylon resin is included in the nylon material of the invention in an amount of at least about 40 percent, preferably at least about 50 percent and even more preferably at least about 60 percent, based on to the weight of the composite nylon material. The nylon resin is also included in the nylon material in an amount of up to about 90 percent, preferably up to about 80 percent and even more preferably up to about 70 percent, based on the weight of the nylon material compound.

The nylon material of the invention may also comprise a reinforcing agent which may be a fibrous material or a mineral reinforcing agent. Useful fiber reinforcements include, without limitation, glass fibers, carbon and graphite fibers, polymer fibers including aramid fibers, boron filaments, ceramic fibers, metal fibers, asbestos fibers, berilium fibers, silica fibers, carbide fibers silicon, and so on. The fibers can be conductive and these conductive fibers for example, conductive carbon fibers or metal fibers, can be used to produce articles for static or conductive dissipating charge applications or EMI coatings. Among these, glass fibers, carbon fibers and aramid fibers are preferred. Methods for preparing the thermoplastic resins that include these fibers are well known in the art. In one method, the bundles of cut glass fiber are fed into the melting zone of the extruder that is being used to form the reinforced nylon material. Alternatively, the fiber is introduced as a tow or continuous bundle into a port in the extruder.

The reinforcing agent of the invention may also comprise a mineral reinforcing agent. Suitable mineral reinforcing agents include, without limitation, wollstoneta, micas, glass beads (solid or hollow) kaolin and talc. The micas can be treated, for example, with coupling agents such as silanes to improve the mechanical properties or with a nickel layer for special applications. Preferred mineral reinforcing agents are wollastonite, mica, kaolin and talc. Mineral reinforcing agents are typically incorporated into the resin by feeding through a hopper into the melting zone of the extruder.

The reinforcing agent can be and in many cases it is preferred that it be a combination of the reinforcing fibers and the reinforcing minerals. For example, in a preferred embodiment, the reinforcing agent is a combination of glass fibers and wollastonite. The reinforcing agent or agents are included in amounts of at least about 5 percent, preferably at least 15 percent, and even more preferably at least about 25 percent, based on the weight of the composite resin. The reinforcing agent or agents are included in amounts of up to about 70 percent, preferably up to about 60 percent and even more preferably up to about 50 percent, based on the weight of the composite resin. Typically, about 25 percent of about 60 percent of the reinforcing agent is included in the composite nylon.

Suitable thermal stabilizers by the addition of the material of the invention should be phenols and interrupted phosphites. Copper iodide or other stabilizers that paint the materials are not preferred.

The nylon materials may include at least one additional additive. Examples of suitable additives include, without limitation, plasticizers; thixotropes; optical brighteners; antioxidants; UV absorbers and interrupted amine or light stabilizers of interrupted amide; flame retardants; pigments and dyes; process aids such as lubricants, mold release agents and slip agents; the fragrances; anti foam agents; antioxidants; antistatic agents; antimicrobial; biocides and so on. Impact modifiers such as ionomers, maleated elastomers and natural and synthetic rubber particles and other material that would tend to form discrete phases are not preferred.

The nylon composition may include one or more pigments or dyes. Preferably the pigment is present in an amount of up to about 4 percent by weight and especially up to about 2 percent by weight, based on the weight of the resin. Suitable pigments are black, white or color pigments. Examples of useful pigments include, without limitation, titanium dioxide, zinc oxide, zinc sulfide carbon black, iron oxide black, copper chromite black, iron oxide yellow, iron oxide red, iron oxides coffee, ocher, sienna, umber, hematite, limonite, mixed iron oxides, chromium oxide, Prussian blue (ammonium ferrocyanide) chrome green, chrome yellow, manganese violet, cobalt phosphate, cobalt lithium phosphate, ultramarines , green and blue copper phthaloxyanines, azo, purple and gold metallized and non-metallic red quinacridones, monkey and diarylid yellows, naphton reds, pyro-pyroles, anthraquinones, thioindigo, flavantrone and other bat pigments, pigments based on benzimidazolone, diozazine, perylenes, carbazole violet, perinone, isoindoline and so on.

The dyes can be used in place of a pigment or in addition to a pigment. For example, a dye can be used to produce a brighter color than would otherwise be obtained with a composition containing only pigments. Examples of useful dyes include, without imitation, azo dyes, such as Solvent Yellow 14 and Yellow Metanil; Anthraquinone dyes like Solvent Red 111, Solvent Blue 56, and Solvent Green 3; xanthene dyes such as Rhodamine B, Sulfo Rhodamine, Solvent Green 4, Red Acid 52, Basic Red 1, and Solvent Orange 63; azine dyes, such as indulin and nigrosin; Fluorescent dyes, Shiny sulfoflavin (Yellow Acid 7) Solvent Orange 60 (a perch tone) basic triphenyl methane dyes, such as methyl violets and l Victoria Blue B and yellow quinoline.

Conductive materials include conductive pigments such as certain grades of carbon black and graphite. Carbon black can function both as a driving material and as a colorant. These conductive material can be incorporated into the coating composition in accordance with the usual methods of fillers or incorporation pigments, which will generally be described with particular reference to the pigments.

The dry pigment may be added, preferably together with the resin, during the composite of the reinforced nylon material or pre-dispersed in a carrier resin before the composite. The pigment can be dispersed in a component of the carrier resin which is preferably a hydrophobic resin component by a two-step process. In a first step, the pigment agglomerates are broken into smaller particles. In a second step, the air on the surface of the pigment particles is displaced with the resin to "moisten" the pigment and thereby fully develop its shade and color strength. A method for dispersing the pigment in the carrier resin component is to first stir the pigment with the granules of the resin and then obtain an intimate mixture by processing the stirred mixture into rule milling, Banbury mixer, intensive mixer or single or double extruder. screw. The resin component is advantageously selected for its ability to disperse a high pigment load and for its easy handling.

The disperse dye can be, for example, a conventional color concentrate or a liquid color. Typical color concentrates may include one or more thermoplastic resins and one or more pigments. Examples of suitable thermoplastic resins include, without limitation, waxes, polyolefins, nylon homopolymers and copolymers and styrene-based polymers. Suitable waxes include naturally occurring waxes such as animal waxes, vegetable waxes, mineral waxes and petroleum waxes, as well as synthetic waxes. Preferred among these are hydrocarbon waxes such as paraffin waxes; polyalkylene homopolymers and copolymers, especially polyethylene, polypropylene and copolymers of alkenes having from 2 to 10 carbon atoms, particularly copolymers of ethylene with alkenes having from 10 carbon atoms, especially copolymers with microcrystaline waxes of propylene or butelene '; carnuba waxes; montana waxes; Fischer Tropsch waxes; fatty alcohols; fatty acid derivatives, especially those having from about 12 to about 18 carbon atoms, including stearic acid, palmitic acid, lauric acid, myristic acid, oleic acid, linoleic acid, and fatty acid of resin oil; these derivatives include fatty amides and esters of fatty acids; hydrogenated oils, such as hydrogenated castor oil; polyeters including polyalkylene glycols such as polyethylene glycol, polypropylene glycol and block copolymers thereof; polytetrahydrofuran; and mixtures of these. Particularly preferred waxes are polyethylene waxes having molecular weights preferably of at least 2000 and preferably below about 12,000; the waxes carnuba; esters of fatty acids; montana waxes and mixtures of these. The pigment can be any of those known in the art as those named above and mixtures of these pigments. Concentrates of conventional color can be found in the form of pelletsh. , cubes, accounts, wafers and micro accounts. The color concentrates can have a pigment loading of about 10 percent by weight to about 80 percent by weight, typically from about 30 percent by weight to about 60 percent based on the weight of the color concentrate. Preferably the color concentrate has a pigment loading of up to about 80 percent by weight and preferably at least about 50 percent by weight, based on 80 percent by weight and preferably at least about 50 percent by weight. of the weight based on the weight of the color concentrate. The concentration of the pigment will vary depending on the selection of the pigment and carrier. Liquid colors will typically have pigment loads of about 10 percent to about 80 percent.

Alternatively, two or more color concentrates or pigments may be added to the nylon reinforced material during the composite to obtain the desired color. Pigments and color concentrates are readily available commercially in a number of companies, including BASF Corporation, Mount Olive, New Jersey; Cabor Corporation, altha, MA; Degussa AG, Frankfurt, Germany; Reed Spectrum, Holen, MA; Unifor Color Companu, Holland, MI: Americhem Inc., Cuyahoga Falls, OH; and Holland Colors Americas Inc., Richmond, IN.

The nylon and the above thermoplastic polyurethane materials are combined together in a melt process, preferably using a twin screw extruder. The combined hard / soft articles are produced by melting by forming one of the components in the desired shape, followed by the introduction of the second melting component on the first. Preferred methods include 1) over molding, ie, molding the first rigid thermoplastic, allowing it to cool and then molding a layer of the TPU compound on top of it; 2) co-injection molding, that is, melting streams of two materials are injected into a mold cavity, forming a core protection structure without interlayer mixing; 3) co-extrusion; 4) extrusion coating; 5) blow molding) and 6) thermoforming. Preferably, the molding process will be carried out at a temperature of about 190 to about. The thermoplastic polyurethane articles of the invention can be made by introducing the compositions disclosed herein into a molae such as those skilled in the art. the technique to know and subjecting to the composition of the temperatures of the process like those given to know before. The composition will remain in the mold subject to high heat conditions for a sufficient time to result in molded articles.

In general, the nylon thermoplastic material of the invention will have a Shore hardness that is about M 60 to about M 110 on the Roxkwell hardness scale. The hardness of a nylon depends on the type of nylon; the additives in nylon, for example, nucleating agents, plasticizers, glass fibers, etc., and the moisture content of nylon, as shown in the Nylon Plastics Handbock, Melvin Kohan, 1995 Hanser, whose information is incorporated herein by reference.

EXAMPLE 1 A variety of experimental and commercial thermoplastic elastomers (TPEs) were "over-molded" onto Ultramid® B3ZG6 plates and their derived strengths were tested using a 180 ° adhesion test. The results are contained in table 1.

Table 1: results of an adhesion test on the molded TPU plates of Ultramid B3ZG6.

Elastomer Description Shore A thermoplastic hardness 1) Zytel FN 714 PA 6ß-blend of 95 Pebax ethylene copolymer 2533 Polyether block 75 of polyether 3) Lext 2416 PA 6-blend of 85 vulcanized rubber 4) Elastollan C78A-15 TPU-based ester 78 5) Elastollan C60A-10 N TPU, based on ester + 60 phthalate plasticizer 6) Elastollan (*) TPU-based ether + 67 LJ31 / 122 / A rubber 7) Elastollan (+) TPU-based is ether + 80 LP9156 rubber Continuation ... Elastomer Temperature thermoplastic force of the process (° C) adhesion (kN / m) 1) Zytel FN 714 287 1.05 2) Pebax 2533 204 0.27 3) Lext 2416 237 0.23 4) Elastollan C78A-15 193 1.52 5) Elastollan C60A-10 N 193 1.84 6) Elastollan (*) 180 2.91 LJ31 / 122 / A 7 ) Elastollan (*) 180 3.00 LP9156 Ultramid® B3GZ6 is a nylon 6 reinforced 30% glass and modified impact, available from BASF Corp., Mont Olive, New Jersey 1) Zytel FN 714 is available in DuPont, Wilmington DE 2) Pebax 2533 is available in Elf-Atochem, Philadelphia, PA 3) Lext available from Advanced Elastomeric Systems, Inc., Akron OH 4) Elastollan C78A-15 available from BASF Corp., Mt. Olive, NJ 5) Elastollan C60A-10WN available from BASF Corp., Mot.Olive, NJ 6; Elstollan LJ31 / 122 / A available from BASF Corp. Mt. Olive, NJ 7) Elastollan LP91 156 available from BASF Corpo. Mot. Olive, NJ The products of Elastollan® LP9156 and LJ 31/122 / A represent the thermoplastic polyurethanes of the invention, while the products C60A-10WN and C78A-15 are conventional thermoplastic polyurethanes. All thermoplastic polyurethane products that are used in the example are available from BASF Corporation, Mount Olive, New Jersey under the trademark Elastollan®.

The best results were obtained with the thermoplastic polyurethanes of the invention: Elastollan® LP9156 (bond strength = 3.00 kN / m), followed by Elastollan® LJ31 / 122 / A (2.91 kN / m), Elastollan® C60A-10WN (1.84 kN / m), and Elastollan® C78A-15 (1.52 kN / m).

All other tested materials; Zytel® FN (Zytel® is a registered trademark of DuPont de Nemours), Peebax® (Peebax® is a registered trademark of Elf-Atochem), and Lext® (Lext® is a registered trademark of AES) that showed minimal adherence to the nylon under conditions of use.

The results to the adhesion test showed that in general, the materials with good adhesion also exhibited the highest displacement, due to the narrowing / elongation of the elastomeric layer. The TPU of the invention improved to all other materials. Due to its good adhesion, good resistance to thermal aging, abrasion resistance and low Shore hardness without the use of softeners, the two Elastollan® urethanes (LP31 / 122 / A and LP9156) over molded nylon more successfully.

Claims (25)

1. CLAIMS Manufacturing article comprises: (A) a layer of thermoplastic material comprising nylon, wherein the layer of thermoplastic material has a Rockwell hardness of about M60 to about M110, and; (B) a thermoplastic polyurethane blend layer that is capable of adhering to the layer of thermoplastic material, wherein the layer of the thermoplastic polyurethane blend comprises a thermoplastic polyurethane composition comprising: ) 3 to 200 parts of styrene / alpha styrene polymer. metylstyrene / acrylonitrile / alkyl acrylate of 1 to 6 carbon atoms with a glass transition temperature (Tg) below 0 ° C; ) 100 parts of the thermoplastic polyurethane produced from a diisocyanate of a diol of 2 to 10 carbon atoms, and a polyether and / or polyol based on polyester wherein the thermoplastic polyurethane layer has a Shore A hardness of about 65 to about 90 and; wherein the layer of the thermoplastic polyurethane blend is bonded to the layer of the thermoplastic material.
2. 2. The article of claim 1, wherein the article is selected from the group consisting of household energy tools, luggage handles, gear shifts and automobile pedals.
3. 3. The article of claim 1, wherein the layer of the thermoplastic polyurethane blend is bonded to the layer of the thermoplastic material by means of a process selected from the group consisting of overmolding, co-injection molding, co-extrusion , extrusion coating, blow molding and thermoforming.
4. 4. The article of claim 3, molded at a temperature from about 190 to about 230 degrees C.
5. 5. The thermoplastic polyurethane composition of claim 1, further comprising one or more compatibilizing polymers.
6. 6. The thermoplastic polyurethane composition of claim 1, wherein the thermoplastic polyurethane composition is prepared using polyhydroxy compound selected from the group consisting of polyetherols and pliesterols.
7. 7. The thermoplastic polyurethane composition of claim 6, wherein the thermoplastic polyurethane composition is prepared using polyetherols.
8. 8. The thermoplastic polyurethane composition of claim 1, wherein the thermoplastic polyurethane composition is prepared using aromatic isocyanates.
9. 9. The thermoplastic polyurethane composition of claim 1, wherein the thermoplastic polyurethane composition is prepared using diphenylmethane diisocyanate.
10. 10. The thermoplastic polyurethane composition of claim 1, wherein the acrylate terpolymer has a Tg less than 0 degrees C.
11. 11. The thermoplastic polyurethane composition of claim 1, wherein the acrylate terpolymer has from 40 to 85% alkyl acrylate of 1 to 6 carbon atoms.
12. 12. The thermoplastic polyurethane composition of claim 1, further comprising a UV stabilizer comprising one or more materials having an active ingredient selected from the group consisting of stabilizers of the benzotriazole type and stabilizers of the interrupted phenol type.
13. 13. The thermoplastic polyurethane composition of claim 12, wherein the UV stabilizer comprises an active ingredient that is selected from the group consisting of 2- (2-hydroxy-3,5-di-tert-amyl-phenyl) -2H -benzotriazole, 1,6-hexanediylbis (3-benzotriazol-N-yl) -4-hydroxy-5-tert-butyl) propynyl phenyl and mixtures thereof.
14. 14. The thermoplastic polyurethane composition of claim 5, wherein the composition comprises from 1 to 10% of a compatibilizing polymer, as based on the total weight of the components in the thermoplastic polyurethane composition.
15. 15. The thermoplastic polyurethane composition of claim 14, wherein the composition comprises less than 5% of a compatibilizing polymer, as based on the total weight of the components in the thermoplastic polyurethane composition.
16. 16. The thermoplastic polyurethane composition of claim 15, wherein the composition comprises from 2 to 4% of a compatibilizing polymer, as based on the total weight of the components in the thermoplastic polyurethane composition.
17. 17. The thermoplastic polyurethane composition of claim 5, wherein the compatibilizing polymer is an acrylonitrile / styrene copolymer.
18. 18. The nylon of claim 1, wherein the nylon is selected from the group consisting of nylon 6/6, nylon 6, nylon 6/10, nylon 6/12, nylon 4/6, nylon 11, nylon 12, nylon Reinforced glass and reinforced nylon of mineral.
19. 19. The nylon of claim 1, further comprising an additive selected from the group consisting of lubricants, inhibitors, anti-hydrolysis stabilizers, thermal stabilizers, flame retardants, dyes, pigments, inorganic fillers, organic fillers, impact modifiers and reinforcing agents.
20. 20. The nylon of claim 18, further comprising a reinforcing agent selected from the group consisting of glass fibers, carbon fibers and graphite, aramid fibers, boron filaments, ceramic fibers, metal fibers, asbestos fibers , berilium fibers, silica fibers, silicon carbide fibers, wollastonite, micas, glass beads, kaolin and talc.
21. 21. The nylon of claim 20, wherein the reinforcing agent comprises from about 5 to about 70 percent by weight of the nylon. 22. The nylon of claim 21, wherein the reinforcing agent comprises from about 15 to about 60 percent by weight of the nylon. 23. The nylon of claim 22, wherein the reinforcing agent comprises from about 25 to about 50 percent by weight of the nylon. 24. The nylon of claim 18, further comprising an additive selected from the group consisting of plasticizers; thixotropes; optical brighteners; antioxidants; UV absorbers; interrupted amine or light stabilizers of interrupted amide; flame retardants; pigments; colorants; lubricants, mold release agents, slip agents; fragrance; anti-foam agents; antioxidants; antistatic agents; impact modifiers; antimicrobials and biocides.
22. 22. The nylon of claim 18, further comprising a color pigment present in an amount of up to about 14 percent by weight of the nylon.
23. 23. The nylon of claim 22, wherein the pigment is selected from the group consisting of titanium dioxide, zinc oxide, zinc sulfide carbon black, black iron oxide, copper chromite black, iron oxides yellow, red iron oxides, brown iron oxides, ocher, sienna, umber, hematite, limonite, mixed iron oxides, chromium oxide, Prussian blue (ammonium ferrocyanide), chrome green, chromium yellow, manganese violet, cobalt phosphate, cobalt lithium phosphate, ultramarines, green and blue copper phthalocyanines, red azo metallized and non-metallic quinacridones, gold, red and purple, yellow mono- and diarylid, naphthol red, pyrrolo-pyrrole, anthraquinone , thioindigo, flavantrone, pigments based on benzimidazolone, dioxazine, perylenes, carbazole violet, perinone and isoidoiine.
24. 24. The nylon of claim 22, further comprising a dye selected from the group consisting of azo dyes, anthraquinone dyes, xanthene dyes, azine dyes, fluorescent dyes and basic triphenyl tinctures.
25. 25. The nylon of claim 18, which further comprises a dye selected from the group consisting of azo dyes, anthraquinone dyes, xanthene dyes, azine dyes, fluorescent dyes and basic triphenyl dyes. SUMMARY I- I, TNVF.NCTON The present invention provides a process for making articles of manufacture, as well as the articles themselves comprising thermoplastic nylon materials and thermoplastic polyurethane blends capable of adhering to the thermoplastic nylon materials, wherein the thermoplastic polyurethane blends comprise: a) 3 to 200 parts of a styrene / alpha-methylstyrene / acrylonitrile / alkyl acrylate terpolymer of 1 to 6 carbon atoms with a glass transition temperature (Tg) below 0 ° C; b) 100 parts of a thermoplastic polyurethane produced from a diisocyanate, a diol of 2 to 10 carbon atoms and a pcyether and / or polyol based on polyester, and; c) Or 50 parts of various additives including 20 lubricants, pigments, stabilizers, etc. The articles of manufacture can be configured as power tool housings, luggage handles, gear shifts, automobile pedals, etc.