 molding composition, molded part, use of the molding composition, process for producing said molding
专利摘要:
polyoxymethylene with coupled glass fiber. the present invention relates to a molding composition, of a process for the manufacture of said molding composition, obtainable from molded parts, as well as the use of the molding composition for the manufacture of molded parts used in the automobile industry; used in: boxes, locks, winding window systems, wiper systems, pulleys, sunroof systems, seat adjustments, levers, claw gears, enabling pivot, brackets, wiper arms or seat rails. 公开号:BR112013009171B1 申请号:R112013009171 申请日:2011-10-14 公开日:2019-12-17 发明作者:Markgraf Kirsten；Larson Lowell 申请人:Celanese Sales Germany Gmbh；Nutrinova Nutrition Specialties & Food Ingredients Gmbh；Ticona Gmbh； IPC主号:
专利说明:
MOLDING COMPOSITION, MOLDED PART, USE OF MOLDING COMPOSITION, PROCESS FOR THE PRODUCTION OF THE REFERRED MOLDING COMPOSITION AND PROCESS FOR PRODUCTION OF A LONG FIBER REINFORCED MOLDING COMPOSITION The present invention is related to a molding composition, to a process for the production of said molding composition, to molded parts obtained through this process, as well as the use of this composition in the production of molded objects used in the automobile industry, for structures, locks, window lift system, windshield wiper, sunroof, seat adjustment, levers, gears, claws, axle frame or windshield wiper arm. The superior mechanical properties of polyoxymethylene (POM) molding compositions are the reason for their use in numerous applications. To improve their properties, polyoxymethylene homo and / or copolymer are provided with additives to adapt the properties to the application, for example, using reinforcement fibers. The effect of these additives on the properties of the molding composition is affected by the attachment of the additive to the plastic matrix. Attempts to bond the glass fibers to a polyoxymethylene matrix are known in the art. DE 2162345 describes a thermoplastic composition comprising a polyoxymethylene, an isocyanate binding agent and reinforcing glass fibers, where the glass fibers are treated with aminoalkylsilane compounds. The diisocyanate bonding agent is used to improve the compatibility of the polyoxymethylene matrix with the reinforcement fibers. Petition 870190113929, of 11/07/2019, p. 14/84 2/65 Isocyanate binding agents are highly reactive with nucleophilic groups, such as OH or NH2. Therefore, the use of other additives to reinforce polyoxymethylene compositions, which comprise isocyanate based binders, is limited. US patent 2005/0107513 attempts to avoid these problems and uses a catalyst that catalyzes the chemical reaction between the polyacetal polymer matrix and the surface of the additive, i.e., glass fiber. Therefore, the use of a bonding agent is avoided. However, binding agents such as isocyanates are very effective and improve the mechanical properties of fiber-reinforced polyoxymethylene compositions. On the other hand, sensitive additives, which can react with the binding agents, should be avoided. Consequently, additives that reduce formaldehyde emission have not been used in prior art for fiber-reinforced polyoxymethylene molding compositions due to the presence of highly reactive isocyanate bonding agents. Polyoxymethylene (POM) was used to produce long glass fiber composites. Standard POM has demonstrated the same poor adhesion to long glass fiber as seen with short glass fiber. One way to overcome adhesion problems is to use an ethyltriphenylphosphonium bromide catalyst to promote the adhesion of standard POM to long glass fiber, as described in EP-B1-1483333 and US-B27169887. Catalyst technology improves the mechanical strength of POM / long glass fiber composites compared to standard POM / glass fiber composites Petition 870190113929, of 11/07/2019, p. 15/84 3/65 long, but the product has no tensile strength enough for some applications, such as rails in seats for automobiles that require good resistance The traction and good resistance to fatigue per flexion and to Slipping. The object of the present invention is to provide a fiber-reinforced polyoxymethylene composition that demonstrates improved mechanical properties, while having low formaldehyde emission. Another object of the invention is the supply of fiber-reinforced polyoxymethylene compositions that have excellent tensile strength, while having good resistance to flexural fatigue and deformation. It has surprisingly been found that fiber-reinforced compositions that comprise at least one polyoxymethylene with a large amount of hydroxyl groups, at least one bonding agent, at least one reinforcing fiber, and optionally at least one formaldehyde scavenger, leading to the formation of a molding composition that has excellent mechanical properties and low formaldehyde emissions, which are necessary for many applications, especially in the automotive industry, and due to environmental aspects. In addition, the compositions exhibit excellent tensile strength while exhibiting good resistance to flexural fatigue and slip, particularly at high temperatures. One embodiment of the present invention is a molding composition comprising: Petition 870190113929, of 11/07/2019, p. 16/84 4/65 a) at least one polyoxymethylene (A), with terminal OH groups of more than 15 mmol / kg, b) at least one coupling agent (B), c) at least one reinforcement fiber (C) and d) optionally, at least one formaldehyde scavenger (D). Component (A) The molding composition according to the present invention comprises at least one polyoxymethylene (A) having terminal OH groups over 15 mmol / kg (hereinafter referred to as component (A) ”). Component (A) of the molding composition according to the invention is a polyoxymethylene homo and / or copolymer. Preferably, polyoxymethylene (A) has a high content of terminal hydroxyl groups and preferably does not contain low molecular weight constituents or only a small proportion of these. Polyoxymethylene (A) preferably has terminal hydroxyl groups, for example, hydroxyethylene groups (-OCH2CH2-OH) and hemiacetal groups (-OCH2-OH). According to a preferred embodiment, at least 25%, preferably at least 50%, and most preferably at least 75% of the terminal groups of polyoxymethylene (A) are hydroxyl groups, especially hydroxyethylene groups. O content of groups terminals hydroxyl is of no Minimum 80%, based on all the groups terminals. In wake up with the gift invention, the term all the groups terminals ”should be understood as all groups terminals and - if present - all side groups. Petition 870190113929, of 11/07/2019, p. 17/84 5/65 In addition to the hydroxyl end groups, POM may also have other usual end groups for these polymers. Examples of these are alkoxy, formate, acetate or aldehyde groups. According to a preferred embodiment of the present invention, polyoxymethylene (A) is a homo or copolymer of polyoxymethylene which comprises at least 50 mol%, preferably at least 75 mol%, and more preferably at least 90 mol%, and even more preferably at least 95 mol% of CH2O repeating units. It has been found that molding compositions that demonstrate extremely high impact strength can be obtained with a polyoxymethylene (A) that has low molecular weight constituents, with molecular weights below 10,000 daltons, less than 15% by weight, preferably less than 10% by weight, more preferably less than 7% by weight and even more preferably less than 5% by weight, based on the total mass of the polyoxymethylene. The POM polymers "that can be used as polyoxymethylene (A) generally have a melt volume flow (MVR) of less than 50 cm3 / 10 min, preferably ranging from 1 to 50 cm3 / 10 min, preferably also varying 1 to 20 cm3 / 10 min, more preferably ranging from 2 to 15 cm3 / 10 and especially ranging from 4 to 13 cm3 / 10 min, determined according to ISO 1133 at a temperature of 190 ° C and 2 , 16 kg. However, depending on the application of the molding composition and the nature and structure of the reinforcing fibers in the molding composition, a greater flow of molten volume Petition 870190113929, of 11/07/2019, p. 18/84 6/65 (MVR) can be desired. According to an alternative embodiment of the present invention, polyoxymethylene (A) has an MVR of more than 35 cm 3/10 min, preferably ranging from 40 to 100 cm 3/10 min, especially range from 55 to 90 cm 3 / 10 in, determined according to ISO 1133, at a temperature of 190 ° C and 2.16 kg. In addition, the impregnation of long fibers is improved. Preferably, polyoxymethylene (A) has a content of terminal hydroxyl groups of at least 16 mmol / kg, preferably at least 18 mmol / kg, most preferably ranging from 15 to 50 mmol / kg, and even more preferably varying 18 to 40 mmol / kg, especially 20 to 30 mmol / kg. However, depending on the application of the molding composition and the nature and structure of the reinforcement fibers in the molding composition, a higher content of terminal hydroxyl groups may be desired. According to an alternative embodiment of the present invention, polyoxymethylene (A) has a content of terminal hydroxyl groups of at least 40 mmol / kg, preferably at least 55 mmol / kg, most preferably ranging from 60 to 95 mmol / kg , and even more preferably ranging from 70 to 90 mmol / kg, especially ranging from 80 to 85 mmol / kg. It has been found that especially the mechanical performance of long fiber reinforced compositions can be improved through the use of a polyoxymethylene with a high content of terminal hydroxyl groups. In addition, the impregnation of long fibers is improved. The content of terminal hydroxyl groups can be determined as described in K. Kawaguchi, E. Masuda, Petition 870190113929, of 11/07/2019, p. 19/84 7/65 Y. Tajima, Journal of Applied Polymer Science, Vol. 107, 667-673 (2008). The preparation of polyoxymethylene (A) can be carried out by the polymerization of polyoxymethylene-forming monomers, such as trioxane or a mixture of trioxane and dioxolane, in the presence of ethylene glycol as a molecular weight regulator. Polymerization can be carried out as precipitation or in particular during melting. The initiators that can be used are known compounds, such as trifluoromethane sulfonic acid, and are preferably added as a solution in ethylene glycol to the monomer. The procedure and completion of the polymerization and the development of the product obtained can be carried out according to processes known in the art. Through an appropriate choice of polymerization parameters, such as duration of polymerization or amount of the molecular weight regulator, the molecular weight and, consequently, the MVR value of the resulting polymer can be adjusted. The criteria for choosing this aspect are known to those skilled in the art. The procedure described above for polymerization serves as a rule for polymers that have small proportions of low molecular weight constituents. If a further reduction in the content of the low molecular weight constituents is desired or required, it can be accomplished by separating the low molecular weight fractions from the polymer after deactivation and degradation of the unstable fractions after treatment with a basic protic solvent. Petition 870190113929, of 11/07/2019, p. 20/84 8/65 This can be a fractional precipitation of a stabilized polymer solution, with polymeric fractions of different molecular weights being obtained. The polyoxymethylene is preferably polyoxymethylene (A), which is also obtained by the polymerization of polyoxymethylene-forming monomers in the presence of heteropoly acids. In one embodiment, a polyoxymethylene polymer with hydroxyl end groups can be produced using a cationic polymerization process followed by hydrolysis of the solution to remove any unstable end groups. During cationic polymerization, a glycol, such as ethylene glycol, can be used as a chain-finishing agent. Cationic polymerization results in a bimodal molecular weight distribution containing low molecular weight constituents. In one embodiment, low molecular weight constituents can be reduced significantly by conducting the polymerization using a heteropoly acid, such as phosphotungstic acid, as the catalyst. For example, if a heteropoly acid is used as a catalyst, the amount of low molecular weight constituents may be less than 2% by weight. Heteropolyacid is a generic term for polyacids formed by condensation of different types of oxoacids through dehydration, and contains a complex mono or polynuclear ion, where the heteroelement is present in the center, and the oxoacid residues are condensed through oxygen atoms . Such heteropolyacid is represented by the formula: Petition 870190113929, of 11/07/2019, p. 21/84 9/65 Hx [M m M'nOz] yH2O where M represents an element selected from the group consisting of P, Si, Ge, Sn, As, Sb, U, Mn, Re, Cu, Nit, Ti, Co, Fe, Cr, Th and Ce, M 'represents an element selected from the group consisting of W, Mo, V and Nb, m is a number from 1 to 10, n is a number from 6 to 40, z is a number from 10 to 100, x is a number greater than or equal to 1, y is a number from 0 to 50. The central element (M) in the formula described above can be composed of one or more types of elements selected from P and Si, and the coordinate element (M ') is composed of at least one element selected from W, Mo and V, particularly W or Mo. Specific examples of heteropolyacids are selected from the group consisting of phosphomolybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, phosphomolybdedovanadic acid, phosphomolyibdotungstovanadic acid, phosphotungstovanadic acid, silicotungstic acid, silicomic acid and silicomic acid; Excellent results were obtained with heteropoly acids selected from molybdophosphoric acid (H3PMO12O40) and 12-tungstophosphoric acid (H3PW12O40) and their mixtures. The heteropoly acid can be dissolved in an alkyl ester of a polybasic carboxylic acid. Was Petition 870190113929, of 11/07/2019, p. 22/84 10/65 found that alkyl esters of polybasic carboxylic acid are effective for dissolving heteropoly acids or their salts at room temperature (25 ° C). The alkyl ester of polybasic carboxylic acid can be easily separated from the production stream, since no azeotropic mixture is formed. In addition, the alkyl ester of the polybasic carboxylic acid used to dissolve the heteropoly acid or an acid salt thereof complies with safety and environmental aspects, and, in addition, is inert under the conditions for the production of oxymethylene polymers. Preferably, the alkyl ester of a polybasic carboxylic acid is an alkyl ester of an aliphatic dicarboxylic acid of the formula: (ROOC) - (CH2) n - (COOR ') where n is an integer from 2 to 12, preferably from 3 to 6 and R and R 'independently represent an alkyl group having 1 to 4 carbon atoms, preferably selected from the group consisting of methyl, ethyl, npropyl, iso-propyl, n-butyl, iso-butyl and tert-butyl. In one embodiment, the polybasic carboxylic acid comprises the dimethyl or diethyl ester of the formula mentioned above, such as a dimethyl adipate (DMA). The alkyl ester of polybasic carboxylic acid can also be represented by the following formula: (ROOC) 2 - CH - (CH2) m - CH - (COOR ') 2 where Petition 870190113929, of 11/07/2019, p. 23/84 11/65 m is an integer from 0 to 10, preferably from 2 to R and R 'are independently alkyl groups having 1 to 4 carbon atoms, preferably selected from the group consisting of methyl, ethyl, npropyl, iso-propyl, n-butyl, iso-butyl and tert-butyl. Particularly, the components preferably which can be used to dissolve the heteropoly acid according to the above formula are the butanotetracarboxylic acid tetraethyl ester or butanotetracarboxylic acid tetramethyl ester. Specific examples of the alkyl ester of a polybasic carboxylic acid are selected from the group consisting of glutaric dimethyl acid, adipic dimethyl acid, pyramic dimethyl acid, submeric dimethyl acid, glutaric diethyl acid, adipic diethyl acid, pyelic diethyl acid, submeric acid, phthalic dimethyl, isophthalic dimethyl acid, terephthalic dimethyl acid, phthalic diethyl acid, isophthalic diethyl acid, terephthalic diethyl acid, butanetetracarboxylic acid tetramethyl ester, and tetraethyl ester of butanotetracarboxylic acid, as well as mixtures thereof. Other examples include dimethylisophthalate, diethylisophthalate, dimethyltereftalate or diethyltereftalate. Preferably, the heteropoly acid is dissolved in the alkyl ester of the polybasic carboxylic acid in an amount less than 5% by weight, preferably in an amount ranging from 0.01 to 5% by weight, where the weight is based on the total solution. Petition 870190113929, of 11/07/2019, p. 24/84 12/65 As mentioned earlier, the term polyoxymethylene comprises homopolymer of formaldehyde or its cyclic oligomers, such as trioxane or 1,3,5,7 tetraoxycyclooctane and its corresponding copolymers. For example, the following components can be used in the polymerization process: ethylene oxide, propylene 1,2-oxide, butylene 1,2-oxide, butylene 1,3-oxide, 1,3-dioxane, 1, 3-dioxolan, 1,3-dioxepan and 1,3,6-trioxocane as cyclic ethers, as well as linear oligo- or polyforms, such as polydioxolane or polydioxepane. Functionalized polyoxymethylenes, which are prepared by copolymerizing trioxane and formal trimethylolpropane (ester), and the alpha and beta isomers of formal glycerol (ester) or trioxane and formal 1,2,6-hexanthriol (ester), can be used like polyoxymethylene (A). Such polyoxymethylene homo or copolymers (POM) are known to those skilled in the art and described in the literature. The molding composition of the present invention preferably comprises polyoxymethylene (A) in an amount of up to 95% by weight, preferably ranging from 40 to 90% by weight, more preferably from 55 to 85% by weight, where the weight is based on the total weight of the composition. Component (B) As another component, the molding composition of the present invention comprises at least one coupling agent (B). The bonding agent offers a bond between the polyoxymethylene (A) and the reinforcement fiber and / or the coating / adhesion material surrounding the reinforcement fiber (C). Petition 870190113929, of 11/07/2019, p. 25/84 13/65 Initially, any binding agent capable of reacting with nucleophilic groups, such as -OH or -NH2, can be used. The bonding agent improves the compatibility of the reinforcement fibers (C) with the polymeric matrix. A suitable coupling agent (B) is a polyisocyanate, preferably organic diisocyanate, more preferably a polyisocyanate selected from the group consisting of aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic diisocyanates and mixtures thereof. Polyfunctional binding agents are preferred, such as trifunctional or bifunctional agents. Preferably, the polyisocyanate is a diisocyanate or triisocyanate, which is most preferably selected from 2,2'-, 2,4'-, and 4,4 '- diphenylmethane diisocyanate (MDI); 3.3 '- dimethyl - 4.4' - biphenylene diisocyanate (TODI); toluene diisocyanate (TDI); Polymeric MDI; 4.4 '- carbodiimidamodified liquid diphenylmethane diisocyanate; para-phenylene diisocyanate (PPDI); meta-phenylene diisocyanate (MPDI); 4.4 '- methane triphenyl triisocyanate and 4.4 ”methane triphenyl triisocyanate; 1.5 - naphthalene diisocyanate; 2,4'-, 4,4'-, and 2,2 biphenyl diisocyanate; polyphenylene polymethylene polyisocyanate (PMDI) (also known as polymeric PMDI); mixtures of MDI and PMDI; ethylene diisocyanate; Propylene 1,2-diisocyanate; trimethylene diisocyanate; butylene diisocyanate; bitolylene diisocyanate; tolidine diisocyanate; Tetramethylene 1,2-diisocyanate; Tetramethylene 1,3-diisocyanate; 1.4 Petition 870190113929, of 11/07/2019, p. 26/84 14/65 tetramethylene diisocyanate; pentamethylene diisocyanate; Hexamethylene 1,6-diisocyanate (HDI); octamethylene diisocyanate; decamethylene diisocyanate; 2,2,4 - trimethylexamethylene diisocyanate; 2,4,4 - trimethylexamethylene diisocyanate; 1.12 dodecane diisocyanate; dicyclohexylmethane diisocyanate; 1,3 - cyclobutane diisocyanate; 1.2 cyclohexane diisocyanate; 1,3 - cyclohexane diisocyanate; 1,4 - cyclohexane diisocyanate; diethylidene diisocyanate; methylcyclohexylene diisocyanate (HTDI); 2,4 - methylcyclohexane diisocyanate; 2,6 - methylcyclohexane diisocyanate; 4.4 'diisocyanate - dicyclohexyl; 2,4 '- dicyclohexyl diisocyanate; 1,3,5 - cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate; 1 isocyanate - 3,3,5 - trimethyl - 5 isocyanatomethylcyclohexane; isocyanatoethylcyclohexane isocyanate; bis (isocyanatomethyl) - cyclohexane diisocyanate; 4.4 '- bis (isocyanatomethyl) dicyclohexane; 2,4 '- bis (isocyanatomethyl) dicyclohexane; isophorone diisocyanate (IPDI); dimeryl diisocyanate, 1.12 - dodecane diisocyanate, 1.10 - decamethylene diisocyanate, 1.2 cyclohexylene diisocyanate, 1.10 - decamethylene diisocyanate, 2.4 - 1 - chlorobenzene diisocyanate, furfurilidene diisocyanate, 2 , 4,4 - hexamethylene trimethyl diisocyanate, 2,2,4 - hexamethylene trimethyl diisocyanate, dodecamethylene diisocyanate, 1,3 cyclopentane diisocyanate, 1,3 - cyclohexane diisocyanate, 1,3 - cyclobutane diisocyanate, 1, 4 cyclohexane diisocyanate, 4.4 '- methylenebis (cyclohexyl Petition 870190113929, of 11/07/2019, p. 27/84 15/65 isocyanate), 4,4 '- methylenebis (phenyl isocyanate), 1 methyl - 2,4 - cyclohexane diisocyanate, 1 - methyl - 2,6 cyclohexane diisocyanate, 1,3 - bis (isocyanate - methyl) cyclohexane , 1,6 - diisocyanate - 2,2,4,4 - tetra methylexane, 1,6 - diisocyanate - 2,4,4 - tetra trimethylexane, 1,4 - trans-cyclohexane diisocyanate, 3 isocyanate - methyl - 3, 5.5 - trimethylcyclohexyl isocyanate, 1 - isocyanate - 3.3,5 - trimethyl - 5 isocyanatomethylcyclohexane, cyclohexyl isocyanate, 4.4 ' - dicyclohexylmethane diisocyanate, 1,4 - bis (isocyanatomethyl) cyclohexane, m-phenylene diisocyanate, m - xylylene diisocyanate, mtetramethylxylylene diisocyanate, p - phenylene diisocyanate, p diisocyanate, p '- biphenyl, 3,3' - dimethyl - 4.4 'biphenylene diisocyanate, 3.3' diisocyanate - dimethoxy - 4.4 '- biphenylene, 3.3' - diphenyl - 4.4 '- biphenylene diisocyanate, 4.4' diisocyanate - biphenylene, 3.3 'dichloro - 4.4' - biphenylene diisocyanate, sodium diisocyanate 1,5 - naphthalene, 4 - chlorine - 1,3 - phenylene diisocyanate, 1,5 - tetrahydronaphthalene diisocyanate, metaxylene diisocyanate, 2,4 - toluene diisocyanate, 2,4 '- diphenylmethane diisocyanate, 2,4 - chlorophenylene diisocyanate, 4.4 '- 4.4' diisocyanate - diphenylmethane, p, p '- diphenylmethane diisocyanate, 2.4 - tolylene diisocyanate, 2.6 - tolylene diisocyanate, 4.4' diisocyanate 2.2 - diphenylpropane, 4.4 '- toluidine diisocyanate, dianidine diisocyanate, 4.4' diphenyl diisocyanate, 1.3 - xylylene diisocyanate, 1.4 - naphthylene diisocyanate, 4.4 '- diisocyanate Petition 870190113929, of 11/07/2019, p. 28/84 16/65 azobenzene, 4,4 '- diphenyl sulfone diisocyanate, or mixtures thereof. Especially preferably, they are aromatic polyisocyanates, such as 4,4 '- diphenylmethane diisocyanate (MDI). The molding composition of the present invention comprises the coupling agent (B) preferably in an amount ranging from 0.1 to 5% by weight, more preferably from 0.2 to 3% by weight, and even more preferably ranging from 0.3 to 1.5% by weight, where weight is based on the total weight of the composition. Component (C) Another component of the composition of the present invention is at least one reinforcement fiber (C). The reinforcing fibers that can be used are advantageously produced from mineral fibers, such as glass fibers, polymeric fibers, in particular high modulus organic fibers, such as aramid fibers, or metallic fibers, such as steel fibers, or carbon fibers or natural fibers, such as fibers from renewable sources. These fibers can be in a modified or unmodified form, for example, provided with a coating / adhesion treatment, or chemically treated, to improve adhesion to plastic. Fibers in glass are at particularly preferably.Glass fibers are supplied with one treatment in coating / adhesion to protect the fiber in glass, smooth the fiber, but also to improve the adhesion between the fiber and the matrix material. This treatment generally comprises Petition 870190113929, of 11/07/2019, p. 29/84 17/65 silanes, film-forming agents, lubricants, wetting agents, adhesive agents, optionally antistatic and plasticizing agents, emulsifiers and optionally additives. Specific examples of silanes are aminosilanes, for example, 3 - trimethoxysilylpropylamine, N - (2 - aminoethyl) - 3 - aminopropyltrimethoxy - silane, N - (3 trimethoxysilanylpropyl) ethane - 1,2 - diamine, 3 - (2 aminoethyl - amino) propyltrimethoxysilane, N - [3 (trimethoxysilyl) propyl] - 1,2 - ethane - diamine. Film-forming agents are, for example, polyvinylacetates, polyesters and polyurethanes. Coating / adhesion treatments based on polyurethanes can be used advantageously. The reinforcement fibers can be composed in the polyoxymethylene matrix, for example, in an extruder or kneader. However, the reinforcement fibers can also advantageously take the form of continuous filaments coated or impregnated with the polyoxymethylene molding composition in a process suitable for this purpose, and then processed or finished in the form of a continuous tape, or cut to size of suitable granule, so that the fiber and granule sizes are identical. An example of a process particularly suitable for this purpose is the pultrusion process. According to the invention, the polyoxymethylene molding composition with long reinforced fibers can be a bundle of glass fibers that has been coated with one or more layers of the polyoxymethylene polymeric matrix, so that the fibers have not been impregnated, and The Petition 870190113929, of 11/07/2019, p. 30/84 18/65 mixing of fibers and polyacetal matrix polymer does not occur before processing, for example, through injection molding. However, the fibers were advantageously impregnated with a polyacetal polymer matrix. According to a preferred embodiment, the molding composition of the present invention comprises at least one reinforcing fiber which is a mineral fiber, preferably a glass fiber, more preferably a coated or impregnated glass fiber. Glass fibers that are suitable for the molding composition of the present invention are commercially available, for example, Johns Manville, ThermoFlow® 753 cut tape, OCV Chopped Strand 408 A, Nippon Electric Glass Co. (NEG) Chopped Strand T-651. The reinforcing fibers are preferably present in the molding composition of the present invention in an amount ranging from 5 to 50% by weight, preferably 7 to 45% by weight, and especially preferably from 10 to 40% by weight, where the weight is based on the total weight of the composition. It has surprisingly been found that long fiber reinforced molding compositions have better mechanical properties compared to short fiber reinforced compositions. In addition, the molding compositions of the present invention with long fiber reinforced polyoxymethylene still demonstrate improved resistance to flexural fatigue and deformation of molded products. The bonding agent reacts with the active leaving groups of the POM polymer and with the coating / adhesion treatment on the fiberglass to bond Petition 870190113929, of 11/07/2019, p. 31/84 19/65 chemically the POM to fiberglass. The chemical bond prevents the separation of the POM from the fiberglass, which is common for the standard POM, due to the low adhesion between it and the fiberglass. The reinforced bond between the POM matrix and the long glass fibers significantly improves the mechanical strength of the fiberglass / POM composites. According to a preferred embodiment of the invention, the reinforcement fibers can also advantageously be impregnated or coated in the form of continuous filament fibers with the remaining parts of the molding composition (polymeric matrix), as defined in the present invention, that is, at least one polyoxymethylene (A) having terminal OH groups of more than 15 mmol / kg, at least one coupling agent (B), and the other optional components, such as at least one formaldehyde scavenger (E) and / or others Additives, in a suitable process, are conducted or processed in the form of a continuous ribbon, or cut to a desired granule size, so that the fiber and granule sizes are the same. An example of a process particularly suitable for this purpose is the pultrusion process. In a preferred embodiment of the invention, the long fiber reinforced molding composition of the invention is prepared through the pultrusion process, where i) five beams are conducted through a matrix loaded with a molten material produced from a polymeric matrix comprising at least one polyoxymethylene (A), at least one coupling agent Petition 870190113929, of 11/07/2019, p. 32/84 20/65 (B), and other optional components, such as at least one formaldehyde scavenger (E), ii) the immersed fiber bundles are preferably conducted through a molding matrix, iii) the fiber bundles are optionally cooled, iv) the fiber bundles are optionally post-formed, and v) the fiber bundles are cut to the length of the structure preferably substantially perpendicular to its processing direction, or are finished in the form of a continuous structure. The impregnation of the fiber bundles with the polymeric matrix, for example, via pultrusion in step i) of the above process, can also occur through other suitable processes. For example, fibers can be impregnated by a process where the bundle of fibers is saturated by the polymeric matrix, where the bundle of fibers is placed on the conveyor, and where the conveyor together with the bundle of fibers is conducted through the impregnation equipment. Such a process is described in EP-A-756 536. The fiber can also be impregnated by a process in which a plasticizer extruder is used, and a bundle of fibers is guided through the opening guide and preheating equipment, and is moistened with a liquid polymer matrix film in a device. of impregnation, and then it is introduced into the extruder with plasticizer where the individual fibers are cut and mixed, with the mixture being dispensed in the form of a fiber reinforced polymeric composition of the invention, which Petition 870190113929, of 11/07/2019, p. 33/84 21/65 can be submitted to processing, where the following steps can be used: a) passage through the coating nozzle to the extruder inlet with plasticizer, preferably parallel to the extruder axis, and approximately tangentially, the fiber bundle is guided in an extruder screw and around the screws forward, and also in the cylinder extruder, whose diameter has been increased by at least four times the thickness of the fiber bundle, where b) preferably at the entrance, the coating nozzle on the right side applies a polymeric film on one side of the fiber bundle, while application on the second side occurs indirectly by pressing the bundle into the liquid film of the polymer matrix previously applied to the left side nozzle. , where individual continuous filament fibers are subjected to impregnation or penetrate the extruder screws on both sides of the fiber bundle, and these sides are moistened or saturated by the liquid films of the thermoplastic polymer, c) and then the bundle of fibers or the individual fibers completely saturated or impregnated with the polymeric matrix are released from the inlet and the impregnation section to a discharge and transport section of a reduced diameter cylinder, and then cut to pre-lengths -determined. An example of such a process is described in DE-A-1 98 36 787. The described sustainable and low cost process preferably offers a small structure in the form of Petition 870190113929, of 11/07/2019, p. 34/84 22/65 baton. The length of the structure is 3 to 100 mm, preferably 4 to 50 mm, and particularly preferably 5 to 15 mm. The diameter of the structure, also called pellet, is generally 1 to 10 mm, 2 to 8 mm, and particularly preferably 3 to 6 mm. Another embodiment of the present invention is a process for the production of a long fiber reinforced molding composition comprising a) impregnation of a filament of continuous fibers with a polymeric matrix comprising i) at least one polyoxymethylene (A) with OH terminal groups of more than 15 mmol / kg, i) at least one coupling agent (B), and iii) optionally at least one scavenger of formaldehyde (D) and / or other additives; and b) optional cutting of the filaments of fibers impregnated in pellets. Preferably, the polymeric matrix is mixed by melting before impregnating the filament of the continuous fibers. The continuous fiber filament has been described above. Preferably, the filament of continuous fibers is part of slightly twisted strands or wicks. The process of the invention preferably uses a slightly twisted wire or wick. The polyoxymethylenes (A) that can be used have been defined above. According to a preferred embodiment of the process of the invention, polyoxymethylene (A) has an MVR of more than 35 cm3 / 10 min, preferably ranging from 40 to 100 cm3 / 10 min, especially ranging from Petition 870190113929, of 11/07/2019, p. 35/84 23/65 to 90 cm3 / 10 min, determined according ISO 1133 at a temperature of 190 ° C and 2.16 kg. Polyoxymethylene (A) preferably has a content of terminal hydroxyl groups of at least 40 mmol / kg, preferably at least 55 mmol / kg, and more preferably ranging from 60 to 95 mmol / kg, and even more preferably varying 70 to 90 mmol / kg, especially ranging from 80 to 85 mmol / kg. The process molding compositions preferably comprise: to 90% by weight of polyoxymethylene (A), 0.1 to 5.0% by weight of the coupling agent (B), which is preferably a polyisocyanate; and 45% by weight of the continuous fiber filament, preferably a twisted glass fiber wick. The preferred process is one of pultrusion. According to an embodiment of the present process, polyoxymethylene (A) is mixed by melting with a binding agent, such as a diisocyanate, and stabilizers in an extruder. The long glass fiber (filaments of continuous fibers) is pulled through a matrix where the fiber is impregnated with the molten resin. The concentration of the glass in the final product is controlled by adjusting the amount of resin that is left in the glass fiber when it leaves the matrix. The bonding agent reacts with the active terminal groups of the POM, and the coating / adhesion treatment on the glass fiber chemically bonds the POM to the glass fibers. Component (D) Another component of the molding composition of the present invention that may optionally be present is a Petition 870190113929, of 11/07/2019, p. 36/84 24/65 formaldehyde scavenger (D). Formaldehyde scavengers are additives to remove formaldehyde. Suitable scavengers are stabilizers that contain nitrogen. Most of these compounds are heterocyclic having at least one nitrogen atom as a heteroatom, adjacent to a substituted amino carbon atom or a carbonyl group, for example, pyridine, pyrimidine, pyrazine, pyrrolidone, aminopyridine and derivative compounds. Advantageous compounds of this nature are aminopyridine and derivative compounds. Any aminopyridine is initially suitable, for example, 2,6-diaminopyridine, dimeric and substituted aminopyridines, and mixtures prepared from these compounds. Other advantageous materials are polyamides and diciano-diamides, urea and its derivatives, as well as pyrrolidone and derived compounds. Examples of suitable pyrrolidones are imidazolidinone and derivative compounds, such as hydantoins, derivatives that are particularly advantageous, and those particularly advantageous among the compounds are allantoin and its derivatives. Other particularly advantageous compounds are triamine - 1,3,5, - triazine (melamine) and its derivatives, such as melamine-formaldehyde condensates and methylol melamine. A particular preference is for melamine, methylol melamine, melamine-formaldehyde condensates, and allantoin. Oligomeric polyamides are also in principle suitable for use as formaldehyde scavengers. The formaldehyde scavenger can be used individually or in combination. Petition 870190113929, of 11/07/2019, p. 37/84 25/65 The formaldehyde scavenger (D) can also be a guanidine compound that can include a guanamine-based aliphatic compound, a guanamine-based alicyclic compound, a guanamine-based aromatic compound, a guanamine-based compound containing a heteroatom , or the like. Examples of aliphatic compounds based on guanamine include monoguanamines, such as acetoguanamine, valeroguanamine, caproguanamine, heptanoguanamine, capryloguanamine or stearoguanamine; alkylene bisguanamines, such as succinoguanamine, glutaroguanamine, adipoguanamine, pimeloguanamine, suberoguanamine, azeloguanamine or sebacoguanamine. Examples of guanamine-based alicyclic compounds include monoguanamines, such as cyclohexanocarboguanamine, norbornene carboguanamine, cyclohexenocarboguanamine or norbornene carboguanamine; and its derivatives where the cycloalkane residue is substituted with 1 to 3 functional groups, such as alkyl group, hydroxyl group, amino group, acetoamino group, nitrile group, carboxyl group, alkoxycarbonyl group, carbamoyl group, alkoxy group, phenyl group, group cumila or hydroxyphenyl group. Examples of aromatic compounds based on guanamine are monoguanamines, such as benzoguanamine and its derivatives where the phenyl residue is substituted with 1 to 5 functional groups, such as alkyl group, hydroxyl group, amino group, acetoamino group, nitrile group, carboxyl group, carbonyl alkoxy group, carbamoyl group, alkoxy group, phenyl group, cumila group or hydroxyphenyl group (for example, toluguanamine, xyloguanamine, Petition 870190113929, of 11/07/2019, p. 38/84 26/65 phenylbenzoguanamine, hydroxybenzoguanamine, 4 - (4 'hydroxyphenyl) benzoguanamine, nitrilabenzoguanamine, 3,5 dimethyl - 4 - hydroxybenzoguanamine, 3,5 - di - t - butyl 4 - hydroxybenzoguanamine, and the like), naphthoganamine and its derivatives, where the naphthyl residue is replaced with the above functional group; polyguanamines, such as phthaloguanamine, isophthaloguanamine, terephthaloguanamine, naphthalene diguanamine or biphenylene diguanamine; aralkyl or aralkylene guanamines, such as phenylacetoguanamine, [beta] - phenylproprioguanamine or xylylene bisguanamine. Examples of the heteroatom-containing guanamine-based compound include guanamines containing acetal group, such as 2,4 - diamino - 6 - (3,3 - dimethoxypropyl - s triazine); dioxan ring-containing guanamines, such as [2 - (4 ', 6' - diamino - s - triazin - 2 '- yl) ethyl] - 1,3 - dioxane or [2 - (4 ', 6' - diamino - s - triazin - 2 '- yl) ethyl] - 4 - ethyl - 4 - hydroxymethyl - 1,3 - dioxane; tetraoxospiro ring-containing guanamines, such as CTUguanamine or CMTU-guanamine; guanamines containing isocyanuric ring, such as 1,3,5 - tris (2 - (4 ', 6' - diamino - s - triazin - 2 '- yl) ethyl) isocyanurate or 1,3,5 - tris [3 - (4', 6 '- diamino - s - triazin - 2' - yl) propyl] isocyanurate); imidazole ring-containing guanamines, such as guanamine compounds described in JP-A 6-179671 and JP-A 7-10871; imidazole ring-containing guanamines, such as guanamine compounds described in JP-A 47-41120, JPA 3-284675 and JP-A 7-33766; and guanamine compounds described in JP-A 2000-154181, and the like. In addition, guanamine-based compounds include a compound where the hydrogen atom of the amino group of the Petition 870190113929, of 11/07/2019, p. 39/84 27/65 the above-mentioned guanamine-based compound is replaced with an alkoxymethyl group, such as mono to tetra-methoxymethylbenzoguanamine, mono to octa-methoxymethylCTU-guanamine or the like. In addition, these guanamine-based compounds, particularly preferably are guanamine, acetoguanamine, benzoguanamine and CTU-guanamine. Other formaldehyde (D) scavengers that are attached to oligomers or polymers are also suitable. Examples of these groups of formaldehyde scavengers are shown in formula I. R 1 - [X-CO-NH-R 3 -NH-CO-NR 2 -R 4 ] o (I) where R 1 is a moiety comprising 2 to 20 carbon atoms, preferably an aromatic or aliphatic remainder , most preferably the aromatic remainder of a polyhydroxyl or polyamino compound, with at least 2, preferably 2 to 6 amino and / or hydroxyl groups, X is -O or -NR 2 R 2 is H, alkyl, cycloalkyl, aryl or aralkyl, R 3 is alkylene, cycloalkylene, arylene or aralkylene, R 4 is a selected half of formula II, III, IV, V, VI and VII Petition 870190113929, of 11/07/2019, p. 40/84 28/65 where R 5 is H, -CO-CH3 or CO-C6H5, o is an integer ranging from 2 to 6 and p is 1 or 2. In addition, suitable formaldehyde (D) scavengers are imidazolidine-2-one compounds. The imidazolidine-2-one compounds are preferably those with the following formula: where R 1 and R 2 are independently H, C1-C20 alkyl, OR4, -NO2, hydroxyalkyl having 1 to 10 carbon atoms, R 3 is H, C1-C20 alkyl which is a keto, aldehyde, -COOR4, amine or amide group, optionally substituted, or an aromatic ring having 5 to 10 atoms carbon, and R 4 is a C1-C4 alkyl group. Especially preferably imidazolidine-2-one compounds are: Petition 870190113929, of 11/07/2019, p. 41/84 29/65 It has surprisingly been found that aromatic formaldehyde scavengers (D) are very suitable for the molding compositions of the present invention. According to a preferred embodiment of the present invention, the formaldehyde scavenger (D) has a melting point greater than 235 ° C, preferably greater than 250 ° C, more preferably greater than 280 ° C, and even more preferably greater than 300 ° C, and especially greater than 320 ° C. In addition, it was found that the pKa value of the formaldehyde scavenger (D) can influence formaldehyde emission. According to a preferred embodiment, the formaldehyde scavenger (D) has a pKa value ranging from 4.5 to 10, preferably 4.5 to 6.5. In addition, preference is given for a formaldehyde scavenger (D) that has at least one half of triazine. The use of formaldehyde scavengers that comprise at least one half of triazine not only offers excellent formaldehyde-reducing properties, but also positively influences Petition 870190113929, of 11/07/2019, p. 42/84 30/65 mechanical properties of the molding composition. Formaldehyde (D) scavengers that comprise a triazine moiety are selected from the group consisting of guanamine, melamine, N-butylmelamine, N-phenylmelamine, N, Ndiphenylmelamine, N, N-diallymelamine, N, N ', Ntriphenylmelamine, benzoguanamine , acetoguanamine, 2,4- diamino-6- butyl-s-triazine , ameline, 2.4 - diamino - 6 - benzyloxy - s - triazine, 2,4 - diamino - 6 - butoxy - s - triazine, 2.4 - diamino - 6 - cyclohexyl - s - triazine, 2.4 - diamino - 6 - chlorine - s - triazine, 2.4 - diamino - 6 - mercapto - s - triazine, 2,4 - dioxi - 6 - amino - s - triazine, 2 - oxy - 4.6 - diamino - s - triazine, 1.1 - bis (3,5 - diamino - 2,4,6 - triazinyl) methane, 1,2 - bis (3,5 - diamino - 2,4,6 - triazinyl) ethino (other name: succinoguanamine), 1,3 - bis (3,5 - diamino - 2,4,6 triazinyl) propane, 1,4 - bis (3,5 - diamino - 2,4,6 triazinyl) butane, methylene melamine, ethylendimelamine, triguanamine, melamine cyanurate, cyanurate ethylene dimelamine and riguanamine cyanurate. These triazine derivatives can be used alone or combined with two or more compounds. Guanamines and melamines are preferred, with melamine being particularly preferred. Preferred formaldehyde scavengers (D) are hydrazides, more preferably dihydrazides, such as sebacic acid dihydrazide (SDH). Examples of hydrazide compounds that can be used in the present invention as a formaldehyde scavenger (D) include a compound based on aliphatic carboxylic acid hydrazide, a compound based on Petition 870190113929, of 11/07/2019, p. 43/84 Aromatic carboxylic acid hydrazide, a carboxylic acid hydrazide-based compound containing heteroatom, a polymeric carboxylic acid hydrazide-based compound, and the like. These carboxylic acid hydrazides can be used alone or in a combination of two or more. Examples of aliphatic carboxylic acid hydrazide compounds include: monocarboxylic acid hydrazide (lauric acid hydrazide, stearic acid hydrazide, 1,2,3 hydroxystearic acid hydrazide, 4-butane tetracarboxylic acid hydrazide or the like); polycarboxylic acid hydrazide, such as succinic acid mono or dihydrazide, glutaric acid mono or dihydrazide, adipic acid mono, mono or dihydrazide of monoic acid, mono or dihydrazide of submeric acid, mono or dihydrazide of azelaic acid, mono or sebacic acid dihydrazide, or dodecanedioic acid mono or dihydrazide, hexadecane dioic acid mono or dihydrazide, eicosandioic acid mono or dihydrazide, 1.18 - 7.11 - octadecadiene dicarbohydrazide, and the like. Examples of aliphatic carboxylic acid hydrazide compounds include: monocarboxylic acid hydrazides, such as cyclohexane carboxylic acid hydrazide; and polycarboxylic acid hydrazides, such as dimer acid mono or dihydrazide, trimeric acid mono to triidrazide, 1,2 -, 1,3 - or 1,4 dicarboxylic acid mono or dihydrazide, tricarboxylic acid cyclohexane mono to triidrazide , and the like. Examples of aromatic carboxylic acid hydrazide include: Petition 870190113929, of 11/07/2019, p. 44/84 32/65 monocarboxylic acid hydrazides (benzoic acid hydrazide and its functional group replacement products, such as derivatives where functional groups, such as alkyl, hydroxyl, acetoxy, amino, acetoamino, nitrile, carboxyl, alkoxycarbonyl, carbamoyl, alkoxy groups , phenyl, benzyl, cumyl or hydroxyphenyl are replaced by 1 to 5 benzoguanamine phenyl residues (eg o-toluic acid hydrazide, m-toluic acid hydrazide, p-toluic acid hydrazide, 2.4 acid hydrazide 4,4-, 3,5- or 2,5-dimethyl-benzoic, o-, m- or p-hydroxy-benzoic acid hydrazide, acid hydrazide o-, m-, or p- acetoxy - benzoic, hydrazide of acid 4 - hydroxy - 3 - phenyl - benzoic, hydrazide of acid 4 - acetoxy - 3 - phenyl - benzoic, hydrazide of acid 4 - phenyl - benzoic, acid hydrazide 4 - (4 ' - phenyl) benzoic acid, 4 - hydroxy - 3,5 - dimethyl benzoic acid hydrazide, 4 - hydroxy - 3,5 - di - t butyl - benzoic acid hydrazide, 4 - hydroxy - 3,5 - di - t - butylphenyl acid hydrazide - benzoic, and hydroxy acid hydroxy - 3,5 - di - t - butylphenyl - propionic); [alpha] - or [beta] - naphthoic acid hydrazide and its functional substitution products, such as 1 - naphthoic acid hydrazide, 2 - naphthoic acid hydrazide, 3 - hydroxy - 2 - naphthoic acid hydrazide, or 6 - hydroxy - 2 - naphthoic acid; and polycarboxylic acid hydrazides, such as isophthalic acid mono or dihydrazide, terephthalic acid mono or dihydrazide, 1,4 or 2,6 naphthalene dicarboxylic acid, 3,3'-, 3, mono or dihydrazide 4'-, or 4,4'-diphenyldicarboxylic acid, mono or dihydrazide of acid Petition 870190113929, of 11/07/2019, p. 45/84 33/65 dicarboxylic diphenylether, mono or dihydrazide in acid diphenylmethane dicarboxylic, mono or dihydrazide of acid diphenylethane dicarboxylic, mono or dihydrazide of acid diphenoxyethane dicarboxylic, mono or dihydrazide of acid dicarboxylic diphenyl sulfone, mono or dihydrazide of acid diphenylketone dicarboxylic, mono or dihydrazide of acid 4.4 '- dicarboxylic acid, mono or dihydrazide 4.4' ”- quaterphenylcarboxylic, mono to 1,2,4 - tricarboxylic acid triidrazide, pyromelitic acid mono tetraidrazide and acid mono tetrahydrazide 1, 4,5,8 - naphthoic). Examples of a heteroatom-containing carboxylic acid hydrazide compound include: dioxane ring-containing carboxylic acid mono or dihydrazide, such as 5 - methylol - 5 - ethyl - 2 - (1,1 - dimethyl - 2 carboxyethyl) - 1, 3 - dioxane; carboxylic acid hydrazides containing tetraoxo spiro ring, such as 3.9 - bis (2 - carboxyethyl) mono or dihydrazide 2,4,8,10 - tetraoxospiro [5.5] undecane, mono or 3.9 - bis (2 - methoxycarbonylethyl) - 2,4,8,10 - tetraoxospiro [5.5] undecane, mono or dihydrazide of 3.9 - bis (1,1 - dimethyl - 1 - carboxymethyl) - 2,4,8,10 tetraoxospiro [5.5] undecane, or mono or dihydrazide of 3.9 - bis (1,1 - dimethyl - 1 - methoxycarbonylmethyl) - 2,4,8,10 - tetraoxospiro [5.5] undecane; carboxylic acid hydrazides containing isocyanuric ring, such as 1,3,5 - tris [2 carboethyl] mono to 1,3,5 isocyanurate triidrazide or 1,3,5 isocyanurate triidrazide mono - tris (3 - carboxypropyl); and acid hydrazides Petition 870190113929, of 11/07/2019, p. 46/84 34/65 carboxylic containing hydantoin ring, such as 1,3 bis (2 - hydrazinocarbonylethyl) 5 - isopropyl hydantoin. The compounds based on polymeric carboxylic acid hydrazide are exemplified as follows: polymers or copolymers of polymethacrylic acid hydrazides, which can be cross-linked compounds, such as olefin copolymer, vinyl monomer copolymer, styrene copolymer of styrene compound cross-linking of divinylbenzene, or methacrylic bis ester cross-linking compound; polymer described in JP-A 55-145529 and JP-A 56-105905; polyacrylic amino-amide APA ”commercially available from Otsuka Chemical Co., Ltd .; and copolymer described in US Patent 3,574,786. In addition, diciandiamide (DCD) can be used as component (D).Zeolites can also be used as a component (D). According a modality in preference gives present invention, the kidnapper in formaldehyde (D) it presents at least one - NH2, preferably at least two groups - NH2, and more preferably at least three groups - NH2. It has surprisingly been found that excellent performance can be achieved with a formaldehyde scavenger (D) that has a melting point that is at least 10 ° C, preferably at least 20 ° C, more preferably at least 30 ° C, and even more preferably at least 50 ° C higher than the melting point of polyoxymethylene (A). Petition 870190113929, of 11/07/2019, p. 47/84 35/65 The formaldehyde scavenger (D) is preferably melamine. The formaldehyde scavenger (D) is preferably present in the composition in an amount of up to 2% by weight, more preferably in an amount ranging from 0.001 to 1.5% by weight, also more preferably ranging from 0.01 to 1.0% by weight, and even more preferably ranging from 0.05 to 0.5% by weight, and especially varying 0.08 to 0.3% by weight, where weight is based on weight total composition. The materials molding or molds wake up with the invention can optionally be stabilized and / or modified by known additives. Such stabilizers and processing aids used as an additional component (E) are known to those skilled in the art. Component (E) is generally present in an amount of up to 10% by weight, preferably 0.1 to 5% by weight, and more preferably from 0.5 to 3% by weight. Stabilizers are, for example, antioxidants, acid scavengers, UV stabilizers or heat stabilizers. In addition, the impression material or mold may contain processing aids, for example, adhesion promoters, lubricants, nucleating agents, release agents, excipients, or antistatic agents and additives that offer a desired property to the impression material or the mold, such as dyes and / or pigments and / or impact modifiers and / or glass globules and / or additives that provide electrical conductivity; and Petition 870190113929, of 11/07/2019, p. 48/84 36/65 mixtures of these additives, but without limiting the scope of the mentioned examples. The molding composition of the present invention can also comprise one or more tribological modifiers. Several different types of tribological modifiers can be incorporated into the molding composition of the invention. The tribological modifier may comprise, for example, polytetrafluoroethylene particles, molybdenum sulfide particles, calcium carbonate particles, polymeric particles containing an olefin graft copolymer grafted with a polyvinyl or polyether, grafted copolymer particles containing a core elastomeric comprising a polydiene and a rigid graft composed of a methacrylate and / or a methacrylonitrile, ultra high molecular weight polyethylene particles, stearyl stearate particles, wax particles comprising an aliphatic ester wax composed of a fatty acid and an alcohol monohydric, a polyethylene wax, silicon oil, or a starch wax, or mixtures thereof. In general, one or more tribological modifiers can be present in the composition in an amount of about 1% to about 50% by weight, preferably in an amount ranging from about 3 to about 30% by weight. Possible tribological modifiers that can be added to the composition include: (1) 0.1 - 50.0% by weight, preferably 1.0-25% by weight, of a polytetrafluoroethylene powder, (2) 0.1 - 10.0% by weight, preferably 0 , 2-5% by weight, particularly preferably 0.5-2% by weight, of a molybdenum disulfide powder (MoS2), Petition 870190113929, of 11/07/2019, p. 49/84 37/65 (3) 0.1-50.0% by weight, preferably 1.0-25% by weight, of a calcium carbonate powder (chalk), (4) 0.1 - 50% by weight weight, preferably 1.0-25.0% by weight, particularly preferably 2.0-10% by weight, of a copolymer having an olefin polymer as a graft base, grafted with at least one vinyl polymer or an ether polymer, and / or a grafted copolymer that has an elastomeric core based on polydienes and a rigid graft composed of methacrylates and / or methacrylonitriles. Grafted copolymers cited above are described in EP-A-354,802 and EP-A-420,564 or in EP-A-156,285 and EP-A-668,317. A grafted base suitable for grafted copolymers of the first type is provided initially by any olefin polymer or olefin copolymer, for example homopolymers, such as polyethylene or polypropylene, or copolymers derived from ethylenically unsaturated copolymerizable monomers, for example, ethylene copolymers , ethylene-1-butene copolymers or copolymers derived from ethylene and glycidyl methacrylate. Suitable grafted monomers are initially any ethylenically unsaturated monomer having polar groups, or other grafting monomers with polar groups that modify the polarity of the essentially non-polar grafted base, for example, ethylenically unsaturated carboxylic acids, such as methacrylic acid and its derivatives, such as esters , nitriles, or amides, if Petition 870190113929, of 11/07/2019, p. 50/84 38/65 combined with comonomers, such as acrylonitrile or styrene combined with acrylonitrile. A copolymer grafted on the basis of polyethylene or polypropylene grafted with acrylonitrile or with styrene / acrylonitrile is preferred. Products of this type are known and are commercially available. Preferably grafted bases for grafted copolymers of the second type are polybutadiene, polyisoprene, and / or polybutadiene / styrene. Suitable grafted monomers are initially any ethylenically unsaturated monomer. The ethylenically unsaturated monomers with polar groups are preferred. Copolymers grafted on the basis of polybutadiene and coating with two layers composed of polystyrene and polymethacrylate are particularly preferred. (5) 0.1 - 50.0%, preferably from 1.0% to 25.0%, of an ultra high molecular weight polyethylene powder, whose molar mass is> 10 6 g / mol. Products of this type are known and are commercially available. An example is the product GUR 4120 and GUR 4150 from Ticona GmbH, Kelsterbach, Germany, (6) 0.1% - 10% by weight, preferably 0.1 - 5.0% by weight, and particularly preferably 0.5-3% by weight, stearyl stearate, (7) 0.1% - 10% by weight, preferably 0.5 - 5.0% by weight, and particularly preferably 0, 8 - 2.0% by weight of a silicone oil, to prevent the migration of the silicone oil out of the moldings. It is advantageous to use a silicone oil whose molar mass is> 20,000 g / mol. Petition 870190113929, of 11/07/2019, p. 51/84 39/65 Initially, it is possible to use any of the polysiloxanes that are liquid at room temperature (23C), with their molar mass having at least 20,000 g / mol, preferably 25,000 to 300,000 g / mol. The typical viscosities of these silicone oils, at a temperature of 25 ° C, are in the range of 500 to 300.00 mm 2 / s. Dialkylpolysiloxanes are preferred, particularly dimethylpolysiloxanes. (8) 0.1% - 5.0% by weight, preferably 0.5 - 3.0% by weight of an oxidized polyethylene wax, (9) 0.1% - 5.0% by weight, preferably 0.2 - 2.0% by weight of an amide wax, (10) 0.1% - 5.0% by weight, preferably 0.5 - 3.0% by weight of a wax of aliphatic ester composed of a fatty acid and a monohydric alcohol, (11) 0.1% - 5.0% by weight, preferably 0.5 - 3.0% by weight of a polyethylene wax. In a specific embodiment of the present invention, the tribological modifier comprises or consists substantially of ultra high molecular weight polyethylene (UHMW-PE). It has been found that good results can be obtained with molding compositions that comprise binding agents and reinforcing fibers. Ultra high molecular weight polyethylene (UHMW-PE) can be used, for example, in powder form, particularly as a micro powder. The use of UHMW-PE significantly reduces wear and improves sliding properties. UHMW-PE generally has a particle diameter D50 (volume based and determined by light diffusion) in the range of 1 to 5000 pm, preferably 10 to Petition 870190113929, of 11/07/2019, p. 52/84 40/65 500 pm and particularly preferably from 10 to 150 pm, such as 30 to 130 pm or 80 to 150 pm or 30 to 90 pm. UHMW-PE may have an average molecular weight greater than 1.0 x 10 6 g / mol, preferably greater than 2.0 x 10 6 g / mol, more preferably greater than 4.0 x 10 6 g / mol, and especially having an average molecular weight ranging from 1.0 x 10 6 g / mol to 15.0 x 10 6 / mol, and more preferably ranging from 3.0 x 10 6 g / mol to 12, 0 x 10 6 g / mol determined by viscometry. Preferably, the UHMW-PE viscosity value is greater than 1000 ml / g, more preferably greater than 1500 ml / g, especially ranging from 1800 ml / g to 5000 ml / g, as well as ranging from 2000 ml / g ga 4300 mL / g (determined according to ISO 1628, part 3; concentration in decahydronaphthalene: 0.0002 g / mL). In a preferred embodiment, the tribological modifier is a UHMW-PE. Suitable UHMW-PE is available commercially from Ticona GmbH, Germany, under the trade name of GUR®, such as GUR®4120 and GUR®4150. In a preferred embodiment, the ultra high molecular weight polyethylene can be present in an amount of up to 30% by weight, preferably in an amount ranging from 1 to 25% by weight, more preferably ranging from 2.5 to 20% by weight, especially of 4.5 to 15% by weight, such as 5.5 to 12% by weight, for example, 6.5 to 9.5% by weight, where the amount is based on the total weight of the composition. A molding composition especially preferably of the invention comprises: Petition 870190113929, of 11/07/2019, p. 53/84 41/65 a) 40 to 90% by weight, preferably 55 to 85% by weight of one or more polyoxymethylene (s) (A), b) 0.2 to 3.0% by weight, preferably 0.3 to 1.5% by weight of one or more coupling agents (B), preferably an aromatic polyisocyanate, c) 5 to 45% by weight, preferably 10 to 40% by weight, of one or more reinforcement fibers (C), preferably glass fiber and d) optionally 0.05 to 0.5% by weight, preferably 0.08 to 0.3% by weight of one or more formaldehyde scavengers (D), preferably a formaldehyde scavenger having a higher melting point than whereas 235 ° C, preferably a formaldehyde scavenger having a melting point that is at least 10 ° C higher than the melting point of polyoxymethylene (A), and especially preferably melamine or a melamine derivative; where the weight is based on the total weight of the composition. The reaction of the components is generally carried out at temperatures of 100 to 260 ° C, such as from 150 to 220 ° C, and the mixing time is generally from 0.2 to 60 minutes. Another embodiment of the present invention is a process for producing a molding composition of the present invention comprising the following steps: a) melting mixture of a composition comprising at least one polyoxymethylene (A) having OH terminal groups of more than 15 mmol / kg, at least one coupling agent (B) at least one reinforcing fiber (C) and Petition 870190113929, of 11/07/2019, p. 54/84 42/65 optionally, at least one formaldehyde scavenger (D); at a temperature ranging from 120 ° C to 260 ° C, preferably ranging from 120 ° C to 200 ° C, where the melting point of the formaldehyde scavenger (D) is at least 10 ° C higher than the mixing temperature fusion The bands of preference mentioned above together with the composition of the invention are also applied to the process of the invention. Another embodiment of the invention is a molding composition that is obtained by the process of the invention. In one embodiment, the molding composition of the present invention reacts and is mixed before being used in a molding process. For example, in one embodiment, the different components can be melted and mixed in a single or twin screw extruder, at the temperature described above. Tapes can be produced by the extruder which are then pelleted. Before mixing, the polymeric components can be dried to a moisture content of about 0.05% by weight or less. If desired, the pelleted compound can be ground to any suitable particle size, such as in the range of about 100 microns to about 500 microns. Another embodiment of the present invention is a molded part obtained by molding the composition of the present invention. Preferably molded parts are those used in the automotive industry, especially structures, locks, window lifting system, windshield wiper, sunroof, seat adjustment, levers, Petition 870190113929, of 11/07/2019, p. 55/84 43/65 gears, claws, structure in axes or arm of windshield wiper.Molded parts can to be obtained through of molding techniques known in the area, such how extrusion, thermoforming, molding per injection, molding per blowing, rotational molding, and the like. The molding composition of the present invention is especially suitable for use in the production of molded parts used in the automobile industry. Therefore, another embodiment of the present invention is the use of the composition according to the present invention for the production of molded parts in the automobile industry. Because of the excellent mechanical properties and low formaldehyde emission, the molding composition of the invention can be used for many applications, where stiffness, tensile strength and high impact strength are desired. Another embodiment is the use of the composition or molded parts of the present invention for structures, fasteners, window lifting systems, pulleys, windshield wipers, sunroof, seat adjustment, levers, gears, claws, axle structure, wiper arm windshield or seat rails. Due to the high tensile strength of the molding composition of the present invention, the compositions can be used for injection of molded structural parts that require high tensile strength (> 170 MPa), as well as resistance to flexural fatigue and deformation. A typical application of the composition is on car seat rails. Petition 870190113929, of 11/07/2019, p. 56/84 44/65 Examples: The following components were used in the examples: POM 0: 8 MVR cm3 / 10 min; polyoxymethylene with a content of 3.4% by weight of dioxolane comonomer; portion of the terminal OH groups: 6-8 mmol / kg; melting point: 165 ° C POM 1: 8 MVR cm3 / 10 min; polyoxymethylene with a content of 3.4% by weight of dioxolane comonomer; portion of the terminal OH groups: 20-25 mmol / kg; melting point: 165 ° C B: 4.4 '- diphenylmethane diisocyanate (MDI) C: fiber reinforced (NEG ECS 03 T-651H); fiberglass of stipulated size E: additives (antioxidants and nucleating agents) GUR®4120: ultra high molecular weight polyethylene (available from Ticona GmbH, Germany) with the following properties: Average molecular weight: 5.0 x 10 6 g / mol Viscosity value: 2400 mL / g D50: 120 pm GUR®4150: ultra high molecular weight polyethylene (available from Ticona GmbH, Germany) with the following properties: Average molecular weight: Viscosity value: D50: 6 0 pm All components mixed together. For Pfleiderer, Germany) it was 9.2 x 10 6 g / mol 3850 mL / g in addition to the fiberglass were mixed, a ZSK 25MC (Werner & used (temperature range 190 ° C, melting temperature about 210 ° C). The fiber of Petition 870190113929, of 11/07/2019, p. 57/84 45/65 glass was added using a downstream power supply in a suitable position. The screw configuration with compression elements was chosen to perform an effective mixing of the components during extrusion, as well as to obtain an optimal growth of the fiberglass. Unless otherwise stated, all determinations were performed at room temperature (23 ° C). The testing of the prepared molding compositions was carried out according to the following standards: MVR (190 ° C; 2.16 kg): ISO 1133 Charpy notch impact test: determined at a temperature of 23 ° C according to ISO 179-1 / 1eA (CNI); Breaking elongation, breaking stress and stress modulus were determined according to ISO 527; Formaldehyde emission was determined in accordance with VDA 275 (Verband der Automobilindustrie e.V. (VDA), July 1994); A portion of the terminal OH groups in POM was determined as described in K. Kawaguchi, E. Masuda, Y. Tajima, Journal of Applied Polymer Science, Vol. 107, 667-673 (2008). The melting point of polyoxymethylene (POM) was determined with differential scanning calorimetry (DSC); rate of heating of 10 K / min wake up with ISO 11357-1, -2, -3. Tribology (wear rate X steel; Rz = 1 pm) was measured by a plate test with spheres (test MCR 301, v = 100 mm / s, F = 5N) from Anton Paar Germany GmbH. The results are shown in the tables below. Petition 870190113929, of 11/07/2019, p. 58/84 46/65 Table 1: Molding compositions Examples THE B Ç D(melamine) AND(additions)Type % by weight % by weight % by weight % by weight % by weight 1 POM 1 71, 99 0.7 26 0.11 1.2 2(comparative) POM 1 72.69 0 26 0.11 1.2 3(comparative) POM 0 71, 99 0.7 26 0.11 1.2 4(comparative) POM 0 72.69 0 26 0.11 1.2 Table 2 shows the mechanical properties as well as the formaldehyde emissions from examples 1 to 4 Table 2: Effect of MDI on mechanical properties Example1 Example2 ImprovementO0 Example3 Example4 ImprovementO% Breaking stress[MPa] 161 143 12 160 145 10 Elongation at break[%] 3.7 2.7 37 3.1 2.6 19 Notched Charpy test [kJ / m 2 ] 12.9 8.8 47 11.5 9 28 Table 2 demonstrates that the relative improvement in the mechanical properties of a composition comprising POM and glass fibers by the addition of a binder (MDI) is significantly greater for a POM with a large number of terminal OH groups (POM 1) compared to 10 a POM with a smaller number of terminal OH groups (POM 0). The relative improvement in mechanical properties for POM 0 and POM 1 with (according to the invention) and without (comparison) bonding agent with respect to breaking elongation and impact resistance is shown in fig.1 and fig.2. Table 3: Different formaldehyde scavengers (D) Ex. THE B Ç D ANDType % inWeight % inWeight % inWeight Type % inWeight % inWeight 5 POM1 72.19 0.5 26 melamine 0.11 1.2 Petition 870190113929, of 11/07/2019, p. 59/84 47/65 6 POM1 71.79 0.5 26 Benzoguanamine / melamine 0.4 / 0.11 1.2 7 POM1 71.39 0.5 26 Benzoguanamine / melamine 0.8 / 0.11 1.2 The mechanical properties as well as the formaldehyde emissions of the compositions according to examples 5 to 7 are shown in table 4. Table 4 Example 5 Example 6 Example 7 VDA 275 (7d / 1.5 mm)[pm] 6.5 3.0 1.7 Breaking stress [MPa] 153.7 144.6 137.9 Stretchingbreak [%] 3.5 3.0 2.7 Notched Charpy test [kJ / m 2 ] 12.9 10.4 7.5 Table 5: Different amounts of glass fibers (C) Ex. THE B Ç D ANDType % inWeight % inWeight % inWeight Type % inWeight % inWeight 11 POM1 82.99 0.7 15 melamine 0.11 1.2 1 POM1 71.99 0.7 26 melamine 0.11 1.2 12 POM1 55.99 0.7 42 melamine 0.11 1.2 The mechanical properties and formaldehyde emission properties of examples 11, 12 and 1 are shown in table 6. Table 6 Example 11 Example 1 Example 13 Voltage module [MPa] 6340 9610 14730 Breaking stress [MPa] 120.9 161 170.4 Stretchingbreak [%] 4.0 3.7 2.4 Notched Charpy test [kJ / m 2 ] 9.9 12.9 13.7 Table 7: Different formaldehyde scavengers (D) Ex. THE B Ç D ANDType % inWeight % inWeight % inWeight Type % inWeight % inWeight 13 POM1 72.1 0.7 26 - - 1.2 Petition 870190113929, of 11/07/2019, p. 60/84 48/65 14 POM1 71.99 0.7 26 benzoguanamine 0.11 1.2 1 POM1 71.99 0.7 26 melamine 0.11 1.2 15 POM1 71.99 0.7 26 SDH 1 ) 0.11 1.2 16 POM1 71.99 0.7 26 DCD 2) 0.11 1.2 1) sebaceous acid dihydrazide 2) diciandiamide Table 8 Example13 Example14 Example1 Example15 Example16 Module oftension [MPa] 10150 10210 9610 9830 9990 Voltage ofrupture [MPa] 158.9 158.5 161 160.2 162.4 Breaking elongation [%] 3.5 3.5 3.7 3.5 3.4 Notched Charpy test [kJ / m 2 ] 13.7 13.9 12.9 13.1 13.4 VDA 275 (7d / 1.5 mm) [pm] 19.6 14.8 6.9 7.6 11.2 Table 9 shows the molding compositions of the invention (example 17 and 19) as well as comparative examples 18 and 20. The quantities specified in the table for the components are based on the total weight of the composition. The formaldehyde scavenger (D) is melamine. Table 9: Molding compositions with UHMW-PE Ex. A (POM 1) B Ç F (UHMW-PE) D AND% inWeight % inWeight % inWeight Type % inWeight % inWeight % inWeight 17 65.19 0.5 26 GUR®4120 7 0.11 1.2 18 65.69 - 26 GUR®4120 7 0.11 1.2 19 65.19 0.5 26 GUR®4150 7 0.11 1.2 20 65.69 - 26 GUR®4150 7 0.11 1.2 Table 10 shows the mechanical properties as well as the friction and wear properties of examples 17 to 20. Table 10: Mechanical properties of the molding compositions of examples 17 to 20 Petition 870190113929, of 11/07/2019, p. 61/84 49/65 Examples 17 18 19 20 Notched impact Charpy test [kJ / m 2 ] 12.4 8 12.2 8.9 Charpy impact test [kJ / m 2 ] 62.6 39.2 61.3 41.5 Voltage module [MPa] 8800 8500 9400 8400 Breaking stress(5 mm / min.) [MPa] 136 110 140 110 Breaking elongation (5 mm / min.) [%] 3.3 2.3 3.2 2.5 Coefficient of friction 0.288 0.241 0.325 0.265 Wear rate X steel (Rz = 1 pm) [m / h] 13.4 8.6 23.8 12.2 The molding compositions of the present invention (examples 17 and 19) demonstrate a good balance between mechanical properties, such as impact resistance, tensile strength and elongation at break, as well as friction and wear (which are especially important for automobile industry, such as a window or sunroof lift system, for example, pulleys or sliding agents). The molding compositions of the invention also have a low formaldehyde emission 10 which makes the molded parts suitable for interior applications. Table 11 shows the molding compositions of the invention (examples 21, 23 and 25), as well as comparative examples 22, 24 and 26 to 28. The quantities specified in the table for the components are based on the total weight of the composition. The formaldehyde scavenger (D) is melamine. Table 11 Ex. A (POM 1) B Ç F (UHMW-PE) D AND% inWeight % inWeight % inWeight Type % inWeight % inWeight % inWeight 21 66.69 0.5 25 GUR®4120 7 0.11 0.7 22 67.19 - 25 GUR®4120 7 0.11 0.7 23 68.69 0.5 25 GUR®4120 5 0.11 0.7 24 69.19 - 25 GUR®4120 5 0.11 0.7 Petition 870190113929, of 11/07/2019, p. 62/84 50/65 25 70.69 0.5 25 GUR®4120 3 0.11 0.7 26 71.19 - 25 GUR®4120 3 0.11 0.7 27 73.69 0.5 25 - - 0.11 0.7 28 68.19 - 26 GUR®4120 5 0.11 0.7 Table 12 shows the mechanical properties as well as the wear and friction properties of examples 21 to 28. Table 12: Mechanical properties of examples 21 to 28 Examples 21 22 23 24 25 26 27 28 Notched impact Charpy test [kJ / m 2 ] 10.7 7.9 10.7 7.6 11.5 8.3 12.5 5.5 Charpy impact test [kJ / m 2 ] 54.4 34.8 56.4 35.9 61.1 38.8 70 - - Tension modulus (1 mm / min.) [MPa] 8100 7900 8300 8100 8700 8300 9200 8700 Voltage ofbreak(5 mm / min.) [MPa] 121 101 127 108 137 115 150 110 Stretchingbreak(5 mm / min.) [%] 2.9 2.3 3.1 2.2 3.2 2.4 3.5 2.5 Coefficient offriction 0.28 0.25 0.28 0.27 0.30 0.31 0.44 0.28 Wear rateX steel (Rz = 1 pm) [m / h] 11.1 8.8 12.0 10.8 13.5 17.2 50.9 13.3 The molding compositions of the present invention (examples 21, 23 and 25) have a good balance between mechanical properties, such as impact resistance, breaking stress, breaking elongation and friction and wear properties (which are especially important for applications in automobiles, such as a window or sunroof lift system, for example, pulleys and sliding elements). The molding compositions of the invention also demonstrate a very low formaldehyde emission which makes the molded parts suitable for in-car applications. The 15 molding compositions according to the examples Petition 870190113929, of 11/07/2019, p. 63/84 Comparative 51/65 are not balanced in terms of mechanical properties and friction and wear properties. Examples 29 to 35 Examples 29 to 35 below were performed under the following conditions: POM 2: 39 MVR cm3 / 10 min .; polyoxymethylene with a content of 3.4% by weight of dioxolane comonomer; portion of the terminal OH groups: 16-25 mmol / kg; melting point: 165 ° C POM OH: 39 MVR cm3 / 10 min .; polyoxymethylene with a content of 3.4% by weight of dioxolane comonomer; portion of the terminal OH groups: 54-80 mol / kg; melting point: 165 ° C. Phosphonium bromide catalyst: ethyltriphenyl phosphonium bromide Binding agent: 4,4 'diphenylmethane diisocyanate Short glass fiber: NEG EC03 T 651 H Long fiberglass: JM Star Rov 860 The long glass fiber / POM composites were prepared by melting polyoxymethylene with a bonding agent, nucleating agent and a stabilizer (antioxidant), using a 70 mm twin screw extruder. Then, the long glass fiber was pulled through the matrix where the fiber was impregnated with the molten resin. The extrusion conditions that were used to produce the examples, except for example 30, are shown in table 13 below. Table 13 Extruder temperatures ° C Extruder Rate of Extruder velocity Petition 870190113929, of 11/07/2019, p. 64/84 52/65 Barrel area number food of the screw 1 2 3 4 5 6 7 Matrix (kg / h) (rpm) 210 210 210 200 200 200 200 220 70 400 Short glass fiber / POM 1 composites (example 30) were prepared by melting polyoxymethylene with a bonding agent, nucleating agent and a stabilizer (antioxidant), using a 40 mm twin screw extruder. Then, the short glass fiber was fed to the extruder in barrel 6. The extrusion conditions are shown in table 14 below. Table 14 Extruder temperatures ° C Ext. Extruder Barrel area number Food fee. Speed of the screw 1 2 3 4 5 6 7 8 9 Matrix (kg / h) (rpm) 205 205 205 200 200 190 190 190 190 200 91 150 The physical property test was performed using standard ISO tension bars. The tension bars were molded using a D Mag molding machine. The molding conditions are included in table 15 below. Table 15 Barrel range 1 (° C) 177 Barrel range 2 (° C) 182 Barrel range 3 (° C) 188 Nozzle (° C) 193 Cast material (° C) 205 Mobile mold (° C) 80 Fixed mold (° C) 80 Back pressure (psi / kPa) 50 / 344.74 Maintenance pressure (psi / kPa) 11600 / 79979.21 Maintenance pressure (psi / kPa) 35 / 241.32 Cooling time (s) 15 Cycle time (s) 50 Cast cushion (mm) 5 Injection speed (mm / s) 200 Injection time (s) 2 Screw retraction time (s) 10 Examples 29 to 35 were prepared using POM 2 or POM 1 or POM OH, 4.4 'diphenylmethane diisocyanate (bonding agent), stabilizers, nucleating agent, NEG EC 03 T 651 H short glass fiber and fiber glass Petition 870190113929, of 11/07/2019, p. 65/84 53/65 long JM Star Rov 860. The quantity of each component is included in the following table 16. The specified quantities are based on the total weight of the composition. Petition 870190113929, of 11/07/2019, p. 66/84 OK] beautiful 16 Example POM 2 POMOH Phosphonium bromide catalyst Liaison officer Stabilizer Nucleating agent Fiberglass NEG EC30T FiberglassJM Star Rov 860(% by weight) (% by weight) (% by weight) (% by weight) (% by weight) (% by weight) (% by weight) (% by weight) 29 0.0 73.2 0.0 0.0 0.3 0.5 0.0 26.0 30 73.7 ' 0.0 0.0 0.5 0.3 0.5 25.0 0.0 31 72.2 0.0 0.5 0.0 0.3 1.0 0.0 26.0 32 0.0 72.7 0.0 0.5 0.3 0.5 0.0 26.0 33 0.0 59.2 0.0 0.0 0.3 0.5 0.0 40.0 34 0.0 58.7 0.0 0.5 0.3 0.5 0.0 40.0 35 0.0 58.2 0.0 1, 0 0.3 0.5 0.0 40.0 1) For example, POM 1 30 was used. 54/65 Petition 870190113929, of 11/07/2019, p. 67/84 55/65 Physical property data for POM filled with long fiberglass produced using POM OH and without bonding agent (comparative example 29), for improved molding composition with short fiberglass and POM 1, and a diisocyanate bonding agent ( example 30), for POM 2 with long glass fiber produced using ethyltriphenylphosphonium bromide catalyst technology (comparative example 31) and for the molding composition comprising long glass fiber, POM OH and a diisocyanate bonding agent (example 32 ) are included in the table below. Petition 870190113929, of 11/07/2019, p. 68/84 Table 17 Example Voltage ofbreak @ Voltage module in Deformation by Flexural strength Module offlexion Test of23 ° C s Charpy break @Value (MPa) Standard deviation (MPa) Value (MPa) Standard deviation (MPa) Value(%) Standard deviation(%) Value (MPa) Standard deviation(%) Value (MPa) Standard deviation (MPa) Value(kJ / m2) Standard deviation (kJ / m2) Ex 2 9 136 2.80 10406 326 1.7 0.14 205 5.20 9384 222 42.8Ex 3 0 150 0.24 9343 43 3.7 0.07 219 0.85 8806 52 11.6 0.32 Ex 31 163 5.00 9779 295 2.3 0.10 246 7.50 9371 178 30.8 2.90 Ex 32 183 1.20 10603 200 2.3 0.50 283 9.50 9725 275 31.5 56/65 Petition 870190113929, of 11/07/2019, p. 69/84 57/65 The tensile strength of comparative example 29 (without the diisocyanate bonding agent) is 26% less than the strength of the composition of example 32 (with the diisocyanate bonding agent). This indicates that the bonding agent is necessary to bond the reinforcing fiber to the polymeric matrix, causing the improvement of the physical properties of the compositions of the invention. The glass fiber concentration for all long glass fiber samples (examples 29, 31 and 32) is 26% by weight. The glass fiber concentration for the short glass fiber sample (example 30) is 25% by weight. Example 32 of the invention demonstrates improved mechanical performance compared to comparative example 31 and example 30 of the invention. The tensile strength of example 32 is increased by approximately 18% compared to example 30 of the invention (use of short glass fibers), and by around 11% compared to comparative example 31 using POM 2 and fiber long glass, which are prepared using ethyltriphenylphosphonium bromide as a catalyst. The tension modulus is increased by about 8% and the flexural strength is increased by around 13% compared to example 31. The notched Charpy impact strength value for the associated long glass fiber control sample (comparative example 29) is significantly higher than that of the long glass fiber sample (example 32), indicating that there is a better link between the fiberglass and the polymer in the associated sample. The fibers are extracted from the polymer in the control sample (example Petition 870190113929, of 11/07/2019, p. 70/84 58/65 comparative 29) not breaking, which increases the impact resistance of the product. Table 18 below shows the mechanical properties of the compositions according to example 33 (comparative) without a binding agent and example 34 of the invention. The concentration of the fiberglass is increased to 40% by weight. Petition 870190113929, of 11/07/2019, p. 71/84 Table 18 Example Breakdown voltage inThe @ Voltage module in Deformation by Flexural strength Flexural module in Test of23 ° C s Charpy break @Value(MPa) Standard deviation(MPa) Value (MPa) Standard deviation(MPa) Value(%) Standard deviation(%) Value (MPa) Standard deviation(%) Value (MPa) Standard deviation(MPa) Value(kJ / m2) Standard deviation (kJ / m2) Ex 3 3 145 5.6 13407 432 1.4 0.05 225 5.9 13019 300 45.5Ex 34 219 9, 1 14530 349 2.08 0.17 333 7.9 13960 612 37.3 59/65 Petition 870190113929, of 11/07/2019, p. 72/84 60/65 The data in Table 18 demonstrate that increasing the long glass fiber content of the compositions also significantly increases the mechanical performance of the material. A tensile strength of about 220 MPa can be obtained by increasing the load of the fiberglass to up to 40% by weight. This allows the use of materials in applications that require greater tensile strength. The tensile strength of the control sample (example 33) without the diisocyanate binding agent was 34% less than the tensile strength of the associated sample. This is consistent with the results of the samples with 26% by weight of fiberglass, demonstrating that the diisocyanate bonding agent has a significant impact on the improvement of physical properties. Table 19 demonstrates the impact of the amount of the binding agent on the mechanical properties. The amount of the diisocyanate used in the composition according to example 35 is doubled compared to the other examples. Petition 870190113929, of 11/07/2019, p. 73/84 Table 19 Ex. Voltage ofbreak @ Voltage module in Deformation by Flexural strength Flexion module in Test of23 ° C s Charpy break @Value (MPa) Standard deviation (MPa) Value (MPa) Standard deviation (MPa) Value(%) Standard deviation(%) Value (MPa) Standard deviation(%) Value (MPa) Standard deviation (MPa) Value(kJ / m2) Standard deviation (kJ / m2) Ex 3 5 226 2.6 14238 312 2.28 0.1 353 9.7 14025 294 36.6 61/65 Petition 870190113929, of 11/07/2019, p. 74/84 62/65 The data in table 19 indicate that the increase in the binding agent has an effect on flexural strength. It is increased by around 5.7% with the addition of more binding agent. The polymeric adhesion to the long glass fiber was measured for the compositions of examples 30, 31 and 34, to compare the amount of polymeric adhesion with the POM OH bonding degrees of 26% by weight and 40% by weight, with the composition according to comparative example 31 (POM 2, 26% by weight long glass fiber grade, produced using ethyltriphenylphosphonium bromide catalyst). Broken draw bars were evaluated using SEM to determine the percentage of fiber extraction area for each sample. The results are included in the following table 20. Table 20 Example % of fiber extraction area Factor improvement compared to LTF 26% 30 0.0086 2.9 31 0.0253 AT 34 0.0099 2.6 The data in table 20 demonstrate that the polymeric adhesion to the long glass fiber is significantly improved for the samples bound with POM OH and POM 1 compared to the composition of comparative example 31. The area where the fibers were extracted is approximately 2.5 3.0 smaller than that of the samples with POM OH and POM 1. Micrographic SEM for the 3 samples are included in figure 3. The composition according to examples 30, 31 and 34 was also tested using DMA to determine the dynamic sliding behavior of the material during Petition 870190113929, of 11/07/2019, p. 75/84 63/65 the time. Dynamic mechanical analysis (DMA) is an accelerated slip test based on the principle of temperature-time overlap (TTS), which is very useful for comparative studies of long-term properties. The method is described in more detail in Michael Sepe, The Materials Analyst: Part 68A - part 2, published on October 31, 2005. The data from the dynamic mechanical analysis (DMA) of the slip for the compositions at 23 ° C and 80 ° C are presented in the tables below. Petition 870190113929, of 11/07/2019, p. 76/84 Table 21: Slip data at 23 ° C ExampleO Slip load Compliance e @ 1000 h(1 / GPa) Sliding module @ 1000 h (MPa) Sliding module @ 0 h (MPa) Sliding module @ 0.1 h (MPa) Slip module retention * after 1000 h X 0.1 h Slip module retention * after 1000 h X 0 h 31 3 MPa 0.38 2650 6006 4879 44.10% 54.30% 30 3 MPa 0.39 2593 5956 4805 43.50% 54.00% 34 3 MPa 0.27 3686 8210 6353 44.90% 58.00% Table 22: Slip data at 80 ° C ExampleO Slip loadO Compliance @ 1000 h (1 / GPa) Sliding module @ 1000 h (MPa) Sliding module @ 0 h (MPa) Sliding module @ 0.1 h (MPa) Slip module retention * after 1000 h X 0.1 h Slip module retention * after 1000 h X 0 h 31 3 MPa 0.62 1603 4673 3067 34.30% 52.20% 30 3 MPa 0.51 1968 4787 3313 41.10% 59.40% 34 3 MPa 0.37 2732 7315 4942 37.30% 55.30% 64/65 Petition 870190113929, of 11/07/2019, p. 77/84 65/65 The data in tables 21 and 22 indicate that the sliding performance of the samples with POM OH and POM 1, at a temperature of 23 ° C is similar to the composition of comparative example 31 (POM 2, 26% by weight of fiber grade) long glass, using ethyltriphenylphosphonium bromide catalyst). However, the sliding performance is improved in compositions with POM OH and POM 1, according to examples 30 and 34, at a temperature of 80 ° C. In addition, based on the dynamic mechanical analysis (DMA) curves, it can be seen that the slip resistance is improved in the POM OH compositions of the invention, especially at 80 ° C.
权利要求:
Claims (23) [1] 1. Molding composition FEATURED for understanding: a) at least one polyoxymethylene (A), in which at least 25% of the terminal groups of polyoxymethylene (A) are hydroxyl groups, polyoxymethylene (A) being present in an amount ranging from 40 to 90% by weight, where the weight is based on the total weight of the molding composition, b) at least one coupling agent (B), wherein the coupling agent (B) is a polyisocyanate, c) at least one reinforcement fiber (C) and d) optionally, at least one formaldehyde scavenger (D). [2] Molding composition according to claim 1, CHARACTERIZED by the fact that at least 50% of the polyoxymethylene terminal groups (A) are hydroxyl groups. [3] 3. Molding composition according to claim 1 or 2, CHARACTERIZED by the fact that the coupling agent (B) is an organic diisocyanate. [4] 4. Molding composition according to claim 1 or 2, CHARACTERIZED by the fact that the coupling agent (B) is present in an amount ranging from 0.1 to 5% by weight, where the weight is based on the total weight composition. [5] 5. Molding composition according to claim 1 or 2, CHARACTERIZED by the fact that the formaldehyde scavenger (D) is an aromatic compound. [6] 6. Molding composition according to claim 1 or 2, characterized in that it comprises one or more tribological modifiers. Petition 870190113929, of 11/07/2019, p. 79/84 2/5 [7] Molding composition according to any one of claims 1 to 6, CHARACTERIZED in that the reinforcement fiber (C) is a continuous filament fiber. [8] Molding composition according to claim 1 or 2, characterized by further comprising a UV stabilizer and a heat stabilizer. [9] 9. Molded part CHARACTERIZED by being obtained by molding a molding composition, as defined in any one of claims 1 to 8. [10] 10. Use of the molding composition, as defined in any one of claims 1 to 8, or of the molded part, as defined in claim 9, CHARACTERIZED in the production of boxes, latches, locks, window lifting system, pulleys, windshield wiper, sunroof, seat adjustment, levers, gears, claws, axle frame, windshield wiper arm or seat rails. [11] 11. Process for producing a molding composition, as defined in any one of claims 1 to 8, or a molded part, as defined in claim 9, CHARACTERIZED by comprising the following steps: a) melt mix a composition comprising at least one polyoxymethylene (A), in which at least 25% of the terminal groups of polyoxymethylene (A) are hydroxyl groups, polyoxymethylene (A) being present in an amount ranging from 40 to 90% by weight, where the weight is based on the total weight of the molding composition, at least one coupling agent (B), where the coupling agent (B) is a polyisocyanate, Petition 870190113929, of 11/07/2019, p. 80/84 3/5 at least one reinforcement fiber (C) and optionally, at least one formaldehyde scavenger (D); at a temperature ranging from 120 ° C to 260 ° C, where the melting point of the formaldehyde scavenger (D) is at least 10 ° C higher than the melting mixture temperature. [12] 12. Process for producing a molding composition reinforced with long fibers FEATURE for understanding: a) impregnating a filament of continuous fibers with a polymeric matrix comprising i) at least one polyoxymethylene (A), in which at least 25% of the terminal groups of polyoxymethylene (A) are hydroxyl groups, polyoxymethylene (A) being present in an amount ranging from 40 to 90% by weight, in which the weight is based on the total weight of the molding composition, ii) at least one coupling agent (B), where the coupling agent (B) is a polyisocyanate, iii) at least one reinforcing fiber (C) and iv) optionally, at least one formaldehyde scavenger (D), where the melting point of the formaldehyde scavenger (D) is at least 10 ° C higher than the melt mix temperature; and b) optionally cutting the fiber filaments impregnated in granules. [13] 13. Process according to claim 12, CHARACTERIZED by the fact that the polymeric matrix is mixed by melting before impregnating the continuous fiber filament. Petition 870190113929, of 11/07/2019, p. 81/84 4/5 [14] 14. Process according to claim 12 or 13, CHARACTERIZED by the fact that the continuous fiber filament is part of a thread or wick. [15] 15. Process according to any one of claims 12 to 14, CHARACTERIZED by the fact that polyoxymethylene (A) has a content of terminal hydroxyl groups of at least 40 mmol / kg, and the molding composition comprises: 40 to 90% by weight of polyoxymethylene (A), 0.1 to 5.0% by weight of the coupling agent (B), comprising a polyisocyanate; and 5 to 45% by weight of the continuous fiber filament. [16] 16. Process according to any one of claims 12 to 15, CHARACTERIZED as a pultrusion process. [17] 17. Molding composition according to claim 1 or 2, CHARACTERIZED by the fact that polyoxymethylene (A) comprises at least 50 mol% of CH2-O repeat units. [18] 18. Molding composition, according to claim 1 or 2, CHARACTERIZED by the fact that the polyisocyanate is selected from the group consisting of aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic diisocyanates and their mixtures. 19. Composition in molding wake up with The claim 1 or 2, CHARACTERIZED fur fact of formaldehyde scavenger (D) presents a Score in fusion higher than 235 ° C. 20. Composition in molding wake up with The claim 1 or 2, CHARACTERIZED fur fact of Petition 870190113929, of 11/07/2019, p. 82/84 5/5 formaldehyde scavenger (D) has a pKa value ranging from 4.5 to 10. [19] 21. Molding composition according to claim 1 or 2, CHARACTERIZED by the fact that the formaldehyde scavenger (D) has a melting point that is at least 10 ° C higher than the melting point of polyoxymethylene (A). [20] 22. Molding composition according to claim or 2, CHARACTERIZED by the fact that the formaldehyde scavenger (D) is present in the composition in an amount ranging from 0.001 to 1.5 by weight, where the weight is based on the total weight of the composition. [21] 23. Molding composition according to claim 1 or 2, CHARACTERIZED by the fact that the formaldehyde scavenger (D) is melamine. [22] 24. Molding composition according to claim 6, CHARACTERIZED by the fact that the tribological modifier is an ultra high molecular weight polyethylene, having an average molecular weight greater than 1.0 x 10 6 g / mol. [23] 25. Molding composition according to claim 6, CHARACTERIZED by the fact that the tribological modifier is an ultra high molecular weight polyethylene which is present in the molding composition in an amount of up to 30% by weight, on which the amount is based in the total weight of the composition.
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同族专利:
公开号 | 公开日 MX2013004129A|2013-07-29| EP2652001B1|2018-12-26| WO2012049293A1|2012-04-19| CN103228692B|2017-05-31| MX344215B|2016-12-07| US20130331488A1|2013-12-12| US20160257805A1|2016-09-08| BR112013009171A2|2016-07-26| EP2652001A1|2013-10-23| JP2013539810A|2013-10-28| KR101828117B1|2018-02-09| JP5999777B2|2016-09-28| US10731027B2|2020-08-04| US9303145B2|2016-04-05| KR20130141526A|2013-12-26| CN103228692A|2013-07-31| ES2711273T3|2019-04-30|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 US3455867A|1965-04-01|1969-07-15|Celanese Corp|Oxymethylene polymers| US3574786A|1967-12-25|1971-04-13|Asahi Chemical Ind|Polyacetal compositions stabilized with a polymer from a dicarboxylic acid dihydrazide,diamine and urea| GB1331829A|1970-12-22|1973-09-26|Celanese Corp|Oxymethylene polymer-glass fibre compositions| DE2150038C3|1971-10-07|1979-04-12|Hoechst Ag, 6000 Frankfurt|Thermoplastic molding compounds based on polyoxymethylene| JPS4741120Y1|1971-11-01|1972-12-12| US3883468A|1972-12-22|1975-05-13|Basf Ag|Thermoplastic molding compositions| GB1434712A|1973-06-27|1976-05-05|Sumitomo Electric Industries|Preparation of lubricatn-containing synthetic resin composi tions| US3901846A|1974-08-12|1975-08-26|Celanese Corp|Thermoplastic polyoxymethylene molding resins| JPS6211612B2|1979-05-01|1987-03-13|Ootsuka Kagaku Kk| DE2947490A1|1979-11-24|1981-06-04|Hoechst Ag, 6000 Frankfurt|POLYOXYMETHYLENE FIBRIDE AND METHOD FOR THE PRODUCTION THEREOF| JPS631163B2|1980-01-29|1988-01-11|Ootsuka Kagaku Kk| US4469842A|1983-08-01|1984-09-04|Celanese Corporation|Isocyanate-coupled reinforced oxymethylene polymers using improved catalyst system| US4480071A|1983-09-19|1984-10-30|Celanese Corporation|Isocyanate-coupled reinforced oxymethylene polymers| DE3582435D1|1984-01-06|1991-05-16|Mitsui Petrochemical Ind|THERMOPLASTIC RESIN COMPOSITION.| DE3505524A1|1984-03-28|1985-10-10|Hoechst Ag, 6230 Frankfurt|IMPACT MODIFIED POLYOXYMETHYLENE AND MOLDED BODIES MADE THEREOF| US4652594A|1985-10-16|1987-03-24|Celanese Corporation|Glass fiber-reinforced oxymethylene polymer molding compositions having mechanical properties enhanced by amino-formaldehyde resin coupling agents| US4780508A|1987-12-30|1988-10-25|Mobil Oil Corporation|Method of extrusion of compositions of linear polyethylene and polyacetal and films thereof| US4828755A|1988-02-04|1989-05-09|Hoechst Celanese Corporation|Conductive polyacetal composition exhibiting improved flexibility and toughness| JP2854015B2|1988-07-04|1999-02-03|ポリプラスチックス株式会社|Polyacetal resin composition| KR930004058B1|1988-08-12|1993-05-19|폴리플라스틱스 가부시끼가이샤|Polyacetal resin composition and sliding members| JP3043344B2|1989-09-25|2000-05-22|ポリプラスチックス株式会社|Polyacetal resin composition and sliding member| DE69019474T2|1989-11-28|1996-03-07|Asahi Chemical Ind|Wear-resistant polyoxymethylene resin composition and process for its manufacture.| US5156913A|1989-12-11|1992-10-20|Hoechst Celanese Corp.|Glass reinforced acetal polymer products| JPH0733766Y2|1990-03-09|1995-08-02|富士写真光機株式会社|Endoscope treatment tool standing operation device| JPH0692390B2|1990-03-29|1994-11-16|四国化成工業株式会社|4 - -imidazole compound and its synthesis method, and epoxy resin curing method| JPH0710871Y2|1991-10-22|1995-03-15|日本アビオニクス株式会社|Positioning device for fusion welding| JP3789489B2|1992-04-04|2006-06-21|三菱瓦斯化学株式会社|Method for producing impact resistant polyacetal composition| BR9305567A|1992-06-30|1994-12-27|Polyplastics Co|Composition of polyoxymethylene| DE4236465A1|1992-10-24|1994-04-28|Degussa|Polyoxymethylene with improved stability against acids, process for its preparation and use| JPH06179671A|1992-12-14|1994-06-28|Shikoku Chem Corp|New imidazoline compound and method for curing epoxy resin using the same compound| JP2952135B2|1993-06-19|1999-09-20|四国化成工業株式会社|Diamino-s-triazine compound having imidazoline ring and epoxy resin curing agent containing the compound as active ingredient| JPH0733766A|1993-07-23|1995-02-03|Shikoku Chem Corp|Diamino-s-triazine compound having imidazole ring and method for preventing copper from rusting using the same compound| JP3284675B2|1993-07-29|2002-05-20|松下電器産業株式会社|Electronic component mounting method| JP3167225B2|1993-08-24|2001-05-21|ポリプラスチックス株式会社|Polyoxymethylene composition and molded article thereof| JP3339932B2|1993-09-24|2002-10-28|ポリプラスチックス株式会社|Polyolefin resin composition| JP3267417B2|1993-11-18|2002-03-18|三菱瓦斯化学株式会社|Impact resistant polyacetal composition and method for producing the same| EP0668317A1|1994-02-15|1995-08-23|Rohm And Haas Company|Impact modified polyacetal compositions| JP3355615B2|1994-03-02|2002-12-09|日本ポリウレタン工業株式会社|Method for producing polyoxymethylene-polyurethane alloy| DE4413501A1|1994-04-19|1995-10-26|Inst Verbundwerkstoffe Gmbh|Method and device for fiber bundle impregnation| DE69530601T2|1994-10-24|2004-02-19|Asahi Kasei Kabushiki Kaisha|polyoxymethylene| JP3665660B2|1995-01-31|2005-06-29|ダイセル化学工業株式会社|Fiber reinforced thermoplastic resin molded body, method for producing the same, and long fiber reinforced thermoplastic resin structure| WO1997009383A1|1995-09-07|1997-03-13|Asahi Kasei Kogyo Kabushiki Kaisha|Polyoxymethylene resin composition| JP3706225B2|1997-06-16|2005-10-12|ポリプラスチックス株式会社|Polyacetal resin composition for fuel parts| JP3612416B2|1997-12-25|2005-01-19|ポリプラスチックス株式会社|Fiber reinforced polyacetal resin composition| JP3607806B2|1997-12-25|2005-01-05|ポリプラスチックス株式会社|Fiber reinforced conductive polyacetal resin composition| DE19810659A1|1998-03-12|1999-09-16|Basf Ag|Thermoplastic molding materials for use in e.g. rollers, guide bars, slipways and gears| EP0957128B1|1998-05-14|2002-10-09|Mitsubishi Gas Chemical Company, Inc.|Polyoxymethylene resin composition| JP2000154181A|1998-06-10|2000-06-06|Shikoku Chem Corp|New 2-substituted guanamine compound and flame retardant resin composition containing 2-substituted guanamine compound as active component| DE19836787A1|1998-08-13|2000-02-17|Dieffenbacher Gmbh Maschf|Process and plasticizing extruder for the production of fiber-reinforced plastics| JP2000336241A|1999-05-27|2000-12-05|Showa Denko Kk|High-rigidity polyacetal composite material| WO2001009213A1|1999-07-30|2001-02-08|Asahi Kasei Kabushiki Kaisha|Polyacetal block copolymer| JP4741120B2|2000-08-30|2011-08-03|パナソニック株式会社|Non-linear broadcasting system| KR100441686B1|2001-11-21|2004-07-27|에스케이케미칼주식회사|Composition for polyoxymethylene composite resin and product formed therefrom| DE10209420A1|2002-03-05|2003-09-18|Ticona Gmbh|Long fiber reinforced thermoplastic plastic structures| ES2307926T3|2002-03-05|2008-12-01|Ticona Gmbh|POLY MOLDING MASS AND MOLDED BODIES PRODUCED FROM IT.| US6936651B2|2002-12-17|2005-08-30|E. I. Du Pont De Nemours And Company|Compatibility improvement in crystalline thermoplastics with mineral fillers| JP5005159B2|2003-06-04|2012-08-22|ポリプラスチックス株式会社|Polyacetal resin composition| US20050222303A1|2004-04-06|2005-10-06|Cernohous Jeffrey J|Compositions and methods for producing highly filled materials| US20060111473A1|2004-11-23|2006-05-25|Shengmei Yuan|High density polyoxymethylene compositions| DE102005016130A1|2005-04-08|2006-10-12|Ticona Gmbh|Polyoxymethylene compositions, their preparation and use| EP1896543A1|2005-06-08|2008-03-12|E.I. Du Pont De Nemours And Company|Wear resistant high molecular weight polyacetal-ultrahigh molecular weight polyethylene compositions and articles formed therefrom| DE102005035334A1|2005-07-28|2007-02-01|Ticona Gmbh|Low-emission, tribologically modified polyoxymethylene molding compounds and moldings produced therefrom| US8008390B2|2005-09-16|2011-08-30|Ticona Gmbh|Polyoxymethylene molding compositions, their use, and moldings produced therefrom| US7943726B2|2005-12-24|2011-05-17|Ticona Gmbh|Process for preparation of oxymethylene polymers in a homogeneous phase, and use| US8178479B2|2006-05-09|2012-05-15|Interfacial Solutions Ip, Llc|Compatibilized polymer processing additives| JP5468187B2|2006-09-26|2014-04-09|ポリプラスチックス株式会社|Polyacetal resin composition| JP5281239B2|2006-11-27|2013-09-04|ポリプラスチックス株式会社|Polyacetal resin composition and molded article thereof| CN101130621B|2007-09-14|2011-01-12|深圳市科聚新材料有限公司|Enhancing toughening polyoxymethylene composition and method for producing the same| US20110184098A1|2008-03-11|2011-07-28|Mitsubishi Gas Chemical Company, Inc.|Polyacetal resin composition| DE102008018968A1|2008-04-16|2009-10-22|Ticona Gmbh|Polyoxymethylene molding compounds and molded articles and their use| JP4980986B2|2008-05-28|2012-07-18|ポリプラスチックス株式会社|Polyacetal resin composition and molded article thereof| JP2010037445A|2008-08-06|2010-02-18|Polyplastics Co|Polyacetal resin composition and molded article thereof| CN101343396B|2008-08-18|2011-03-02|巨石集团有限公司|Glass fiber reinforced acetal resin composite material| CN102131865A|2008-09-29|2011-07-20|宝理塑料株式会社|Polyacetal resin composition| JP5612262B2|2008-12-24|2014-10-22|ポリプラスチックス株式会社|Polyacetal resin composition| AT551389T|2009-08-07|2012-04-15|Ticona Llc|POLYACETAL COMPOSITION WITH LOW FORMALDEYD EMISSION| CN101759955A|2009-11-26|2010-06-30|苏州市科创聚合物有限公司|High wear-resistant self-lubricating polyoxymethylene and process for preparing same| JP5449029B2|2010-05-26|2014-03-19|三菱エンジニアリングプラスチックス株式会社|Polyacetal resin composition and resin molded product comprising the same| CN102558755A|2010-10-14|2012-07-11|提克纳有限公司|Glass-fiber reinforced polyoxymethylene| WO2012049293A1|2010-10-14|2012-04-19|Ticona Gmbh|Coupled glass-fiber reinforced polyoxymethylene| EP2581408B1|2011-10-14|2015-07-29|Ticona GmbH|Tribologically modified glass-fiber reinforced polyoxymethylene| CN103131124B|2011-11-22|2016-05-04|合肥杰事杰新材料股份有限公司|Can improve the composition and method of making the same of fiberglass-reinforced polyformaldehyde material performance| CN102532798A|2012-02-15|2012-07-04|开封龙宇化工有限公司|Chopped glass fiber enhanced polyformaldehyde material| EP2653497B1|2012-04-17|2015-01-28|Ticona GmbH|Weather resistant polyoxymethylene compositions| WO2014097270A1|2012-12-20|2014-06-26|Ticona Gmbh|Fiber reinforced polyoxymethylene composition with improved thermal properties| WO2016002045A1|2014-07-03|2016-01-07|株式会社島津製作所|Mass spectrometer|WO2012049293A1|2010-10-14|2012-04-19|Ticona Gmbh|Coupled glass-fiber reinforced polyoxymethylene| EP2581408B1|2011-10-14|2015-07-29|Ticona GmbH|Tribologically modified glass-fiber reinforced polyoxymethylene| EP2653497B1|2012-04-17|2015-01-28|Ticona GmbH|Weather resistant polyoxymethylene compositions| CN103772895A|2012-10-25|2014-05-07|黑龙江鑫达企业集团有限公司|Continuous aramid fiber-reinforced polyformaldehyde material and preparation method thereof| US9017800B2|2012-11-08|2015-04-28|Ticona Llc|Polyoxymethylene with improved printability| WO2014093055A1|2012-12-13|2014-06-19|Ticona Llc|Laser-weldable electrostatically dissipative polyoxymethylene based on stainless steel fibers| WO2014097270A1|2012-12-20|2014-06-26|Ticona Gmbh|Fiber reinforced polyoxymethylene composition with improved thermal properties| WO2014105367A2|2012-12-27|2014-07-03|Ticona Llc|Conductive polyoxymethylene based on stainless steel fibers| CN104130566B|2013-06-07|2016-06-22|郑州精益达汽车零部件有限公司|A kind of polyurethane resin BMC and preparation method thereof| CN105793353B|2013-10-21|2019-06-18|提克纳有限公司|Intrinsic low friction polyformaldehyde| KR101519766B1|2013-12-31|2015-05-12|현대자동차주식회사|Polyoxymethylene resin composition| CN106164167B|2014-03-28|2018-10-02|旭化成株式会社|Polyacetal resin composite and its formed body| US10131782B2|2014-09-05|2018-11-20|Sabic Global Technologies B.V.|Polyoxymethylene compositions, method of manufacture, and articles made therefrom| WO2016057988A1|2014-10-10|2016-04-14|Ticona Llc|Processes for cleaning melt processing equipment| JP6619015B2|2015-09-25|2019-12-11|旭化成株式会社|Polyacetal resin composition and molded article thereof| JP2017061644A|2015-09-25|2017-03-30|旭化成株式会社|Resin guide member, polyacetal resin composition for resin guide member, manufacturing method thereof, and manufacturing method of resin guide member| JP2017061649A|2015-09-25|2017-03-30|旭化成株式会社|Polyacetal resin composite composition and molding thereof| JP6563293B2|2015-09-25|2019-08-21|旭化成株式会社|Polyacetal resin composition and molded article thereof| EP3341439A1|2015-09-30|2018-07-04|Celanese Sales Germany GmbH|Low friction squeak free assembly| US11015031B2|2017-06-16|2021-05-25|Celanese Sales Germany Gmbh|Reinforced polyoxymethylene composition with low emissions| KR20190063811A|2017-11-30|2019-06-10|현대자동차주식회사|Polyoxymethylene resin composition and molding inculding the same| CA3067607A1|2019-01-10|2020-07-10|Building Materials Investment Corporation|Liquid applied roofing system with improved water barrier layer| US20210179846A1|2019-12-17|2021-06-17|Ticona Llc|Powder Composition For Three-Dimensional Printing Containing A Polyoxymethylene Polymer|
法律状态:
2018-05-15| B25A| Requested transfer of rights approved|Owner name: NUTRINOVA NUTRITION SPECIALTIES AND FOOD INGREDIEN | 2018-05-22| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]| 2018-05-29| B25D| Requested change of name of applicant approved|Owner name: CELANESE SALES GERMANY GMBH (DE) | 2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]| 2019-12-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]| 2019-12-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/10/2011, OBSERVADAS AS CONDICOES LEGAIS. |
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申请号 | 申请日 | 专利标题 EP10187614|2010-10-14| PCT/EP2011/067992|WO2012049293A1|2010-10-14|2011-10-14|Coupled glass-fiber reinforced polyoxymethylene| 相关专利
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