Reinforced polyamide

Abstract

This invention provides a method for preparing a reinforced polyamide composition exhibiting high fluidity and toughness. [Solution] The method includes (I) a step of mixing the following two components at a temperature of less than 60°C or more than 100°C: (α) at ​​least one reinforcing agent component and (β) at least one siloxane-based component to form a blended composite component, and (II) a step of melt-mixing the following two components at a temperature of more than 200°C: (γ) at least one polyamide and (ε) the blended composite component from step (I) to form a reinforced polyamide composition having increased impact strength.

Description

[Technical Field]

[0001] The present invention relates to a reinforced polyamide composition, and more specifically, the present invention relates to a reinforced polyamide A composition comprising a polyamide, an impact resistance modifier, and an improved reinforced polyamide composition. Reinforced polyambium containing a blend with siloxane-based polymers that provide impact strength and fluidity properties. Regarding composition. [Background technology]

[0002] Nylon is a general term for a family of synthetic thermoplastic polymers composed of polyamides. Polyamide (PA) is a repeating unit linked by amide bonds. The compound consists of at least 85% by weight of amide linkages (-CO-NH-) directly bonded to two aliphatic groups. It is a well-known synthetic thermoplastic polymer based on aliphatic or semi-aromatic polyamides.

[0003] Synthetic processed nylon (or PA) possesses excellent mechanical properties, solvent resistance, and abrasion resistance. Being plastic, nylon material is used for articles / products and parts in a variety of applications. To form it, it can be melt-processed into various fibers, films, or shapes. For example Reinforced nylon composite materials are used in automotive, industrial machinery, consumer, and electronic applications. It can be used for a variety of applications, particularly in the automotive sector, at room temperature and temperatures below room temperature. The impact strength of reinforced nylon needs to be further improved in both cases. However, nylon Nylon has low impact strength with notches, and in particular, it has low toughness in low-temperature environments. This drawback limits further industrial applications of nylon. The industry is looking to improve (increase or enhance) the impact strength performance of reinforced nylon. They are constantly seeking the law.

[0004] Typically, the impact strength performance (or impact resistance) of reinforced nylon is improved impact resistance (IM). The impact resistance is increased by adding an agent or additive to the reinforced nylon. Adding it to nylon is particularly useful in the automotive sector, both at room temperature and below room temperature. This is one way to improve the impact strength of reinforced nylon. Furthermore, it provides more efficient impact resistance. The modifier improves the stiffness / toughness / fluidity balance of the reinforced nylon and its properties. Since it is possible to reduce the cost associated with manufacturing items made from reinforced nylon, To further reduce the weight of the manufactured items, more efficient impact resistance modifications are possible. A good medicine is needed.

[0005] Until now, the impact resistance modifier (IM) mainly used in reinforced nylon has been anhydrous marrow. It was a polyolefin elastomer grafted with maleic anhydride (MAH). ) is as shown in the following general chemical reaction scheme (Scheme (I)) on POE POE and Nylon are reacted through the reaction between grafted anhydride groups and amine-terminated groups in nylon. To improve compatibility with iron, the polyolefin elastomer (POE) framework is used. It will be grafted.

[0006] [ka]

[0007] MAH-grafted POE is required between non-polar polyolefins and highly polar nylon. This achieves good compatibility characteristics. However, the above reaction irreversibly destroys the imide bond. Causing a significant reduction in the fluidity characteristics of the resulting nylon / POE blend composition .

[0008] So far, for example, optimizing the MAH graft ratio of IM, lowering the Tg of POE, and / or providing crosslinking in POE, many efforts have been made to improve the impact strength of reinforced nylon. Most of the efforts involve the design of components of maleic anhydride (MAH)-grafted POE (also abbreviated as "POE-g-MAH"), such as improving the MAH level grafted on POE. However, the industrial efforts mentioned above to optimize both the impact strength and fluidity performance of reinforced nylon compositions have achieved only limited success. abbreviated) components. However, the industrial efforts described above to optimize both the impact strength and fluidity performance of reinforced nylon compositions have met with only limited success. .

[0009] For example, U.S. Patent No. 9,056,982 (B2) and U.S. Patent No. 9,388,312 relate to a thermoplastic composition in the form of pellets or solids comprising 50 wt% to 99 wt% of nylon 6.6 resin, 1 wt% to 50 wt% of a polymer performance improver, and 0.01 wt% to 25 wt% of a silicone-based additive, wherein the silicone-based additive comprises an ultra-high molecular weight siloxane polymer that cannot be regarded as either a gel or an oil, the siloxane polymer is not functionalized, and is non-reactive with polyamide. .

[0010] U.S. Patent Application Publication No. 20140316041 (corresponding to International Publication No. 2014176143 (A 1)) mentions the use of ultra-high molecular weight polydimethylsiloxane (PDMS) as a reinforcing agent in thermoplastic or thermosetting resin systems. Described in the above references ​​​​​​The resin systems include a wide range of polymers and polyamides. Precipitated silica and hyaluronic acid Loomed silica is similarly blended into PDMS. The PDMS filling volume is high, as mentioned above. The amount in the composition disclosed in the literature is in the range of 20% to 80% by weight. The high filler content of MS is due to the poor compatibility between high-polarity polyamide and low-polarity PDMS. It may be harmful to resin systems that use PDMS.

[0011] Chinese Patent No. 110437611(A) concerns a reinforced nylon composite material with ultra-low temperature resistance. The above references mention the following composite materials: glass fiber, lubricant In addition to other additives, amino or epoxy-terminated PDMS is required as a reinforcing agent. Polyolefin elastomers, which are useful as reinforcing agents, are not mentioned. In addition, the above The references describe a high filler amount (e.g., 5% to 12% by weight) of reinforcing agent based on the total composition. It is necessary.

[0012] Chinese Patent No. 102964822(A) describes at least two nylon reinforcing agents. The method of reinforcing nylon involves using vinyl-PDMS containing vinyl groups. It is effective. Hydrogenated silicon oil is also used as a crosslinking agent. The vinyl group is in hydrogenated silicon oil. It must be present in the cross-linked PDMS.

[0013] Chinese Patent No. 111117223(A) pertains to nylon composite materials containing recycled nylon. It refers to automotive bearing materials made from, and the second component polymers of parts 1 to 10 are, Ultra-high molecular weight (Mw) PDMS is used in ultra-high Mw PE, PU, ​​and ethylene-propylene copolymers. It is used in conjunction with the following. The purpose disclosed in Chinese Patent No. 111117223(A) is The objective is to reduce water adsorption in nylon composite materials. (Chinese Patent No. 111117223(A)) The number indicates that it is intended to improve impact strength or fluidity, or in order to improve impact strength or fluidity. The use of PDMS is not mentioned.

[0014] Considering the limitations regarding impact strength provided by known reinforced nylon compositions, Without adversely affecting other properties of reinforced nylon, such as the fluidity of the nylon compound, and without strengthening Without significantly increasing the manufacturing cost of nylon, especially at low temperatures such as below -30°C, It is desirable to further improve the impact strength of synthetic nylon.

[0015] Furthermore, by blending appropriate components to form an improved reinforced nylon composition... Therefore, a novel reinforced nylon compound, material, or composition having improved properties such as increased toughness. It is desirable to provide goods. [Overview of the project]

[0016] In one broad embodiment, the present invention relates to a reinforced polyamide composition comprising (a) at least (b) one polyamide (e.g., a nylon compound) and (b) at least one impact-resistant improvement The agent and (c) the reinforced nylon composition so as to improve the impact strength properties of the reinforced polyamide composition. A blend with at least one liquid low-viscosity siloxane polymer to form a substance This relates to reinforced polyamide compositions, including those mentioned above.

[0017] In another embodiment, the reinforced polyamide composition of the present invention is the total weight of the reinforced polyamide composition. Based on this, at least one polyamide having a concentration of 50% to 98.99% by weight. Component (a) and at least one impact-resistant modified compound having a concentration of 1% to 50% by weight Component (b), which is a good agent composition, and at least It contains component (c), which is a single liquid, low-viscosity siloxane-based polymer.

[0018] In yet another embodiment, the present invention improves impact strength characteristics (for example, by at least 10%). The present invention includes a method for preparing the above-mentioned reinforced polyamide composition exhibiting an increase in the above-mentioned properties.

[0019] In yet another embodiment, the present invention provides the above-mentioned reinforced nylon having improved impact strength characteristics. The invention includes a method for producing a composition.

[0020] In yet another embodiment, the present invention provides the reinforced poly having improved impact strength characteristics. This includes articles manufactured using amide compositions.

[0021] In one or more other embodiments, the present invention is manufactured using the above-mentioned reinforced nylon composition. This includes articles and methods for manufacturing articles.

[0022] Additional features and advantages of embodiments of the present invention are described in the following embodiments for carrying out the invention. It is included, and some parts will be readily apparent to those skilled in the art from the description, or for carrying out the invention. Recognition by practicing the embodiments described herein, including the forms and claims. It will be done. [Modes for carrying out the invention]

[0023] Temperatures as used herein are expressed in degrees Celsius (°C).

[0024] In this specification, "room temperature (RT)" and / or "ambient temperature" are different from those specified. Unless otherwise specified, this refers to a temperature between 20°C and 26°C.

[0025] "Elastomers" possess viscoelasticity (i.e., both viscosity and elasticity) and are comparable to other materials. It is a polymer with relatively weak intermolecular forces, generally low Young's modulus, and high fracture strain. UPAC (International Union of Pure and Applied Chemistry) defines the term "elastomer" as "rubber-like elasticity." It is defined as "a polymer that exhibits [this characteristic]".

[0026] A "polymer" is prepared by polymerizing the same or different types of monomers. It is a polymer compound. Therefore, the general term polymer is "homopolymer" (trace amount) Under the understanding that impurities can be incorporated into the polymer structure, from only one type of monomer (Used to refer to prepared polymers), and the term "interpolymer" This includes copolymers (polymers prepared from two different types of monomers). (used for), terpolymer (polymer prepared from three different types of monomers) (used to refer to), and poly prepared from three or more different types of monomers Contains mer. Trace amounts of impurities, such as catalyst residues, are incorporated into the polymer and / or within the polymer. It may be incorporated. It also includes all forms of copolymers, for example, random, This also includes blocks, etc. Polymers are often made from one or more specific monomers. "and," and "based on" a specific monomer or type of monomer, "containing" a specific monomer content. Although it is sometimes referred to as "possessing," in this context, the term "monomer" refers to a specific monomer. Please note that this refers to polymerization residues, not non-polymerized species. In this specification, polymers are based on "units," which are the polymerization forms of the corresponding monomers. It is mentioned as such.

[0027] The term "composition" refers to a mixture of materials that constitute the composition, and the materials of the composition. This refers to reaction products and decomposition products formed from a material.

[0028] In this specification, "nylon polymer composition" refers to at least one pure nylon polymer A rimer and at least one other component, such as an elastomer, glass fiber, or small molecule. This refers to a combination, mixture, or blend of additives, etc. The above materials are blended. The type of blend used is generally produced by twin-screw extruders or by immersion. These can be advanced, but are not limited to these.

[0029] In this specification, "impact resistance modifier" means a material used to satisfy the physical property requirements of a rigid component. It is added to increase the flexibility, toughness, and impact strength of various plastic resins. It means additive.

[0030] The terms "impact toughness," "impact strength," and "impact resistance" relating to nylon compositions are as defined in this document. In the details, it was evaluated by the impact method described in CHARPY, ISO 179. This refers to the impact strength performance characteristics of a nylon composition. The above terms can be used interchangeably. can.

[0031] In this specification, "room temperature (RT) impact strength" for nylon compositions refers to the impact strength under room temperature conditions. This refers to the impact strength value of the nylon composition tested.

[0032] The terms "comprising," "including," and "having" , and their derivatives are any additional components, processes, or procedures specified herein. Whether or not they are physically disclosed, they are intended to exclude their existence. No. To avoid ambiguity, the use of the term "comprising" is used in patent All compositions claimed, unless otherwise stated, are polymers or not. Furthermore, it may contain any additional additives, adjuvants, or compounds. In contrast, "from this The term "qualitative" refers to all other components except those that are not essential for operability. To exclude any process or procedure from the scope of any subsequent description. The term "consists of" means Exclude any component, process, or procedure that is not explicitly described or enumerated. The term refers to the listed members individually and in any combination unless otherwise specified. It is pointed to by "se". The use of the singular form includes the use of the plural form, and vice versa.

[0033] The numerical range disclosed herein includes all values ​​from the lower limit to the upper limit (lower limit and upper limit). Includes limits. Includes a range that contains explicit values ​​(e.g., 1, or 2, or 3-5, or If the range is 6 or 7, then any subrange between any two explicit values ​​is included. For example, the above range 1-7 could be sub-ranges 1-2, 2-6, 5-7, 3-7, 5-6, etc. include).

[0034] Where used throughout this specification, the following abbreviations are unless otherwise clearly indicated by the context. Unless otherwise specified, it has the following meanings: "=" means "equal to" or "equal to" and "< ">" means "less than", ">" means "greater than", and ≤ means "less than or equal to". In this context, "≧" means "greater than or equal to," "@" means "in," and μm = micrometer. n, g = grams, mg = milligrams, mW / m·K = milliwatts per meter Rubin degrees, L = liter, mL = milliliter, g / mL = grams per milliliter g / L = grams per liter, g / 10min = grams per 10 minutes, kg / m 3 = kilograms per cubic meter, ppm = parts per million by weight, pbw = parts by weight rpm = revolutions per minute, m = meter, mm = millimeter, cm = centimeter Toll, μm = micrometer, mm 2 / s = millimeters per second, min = minute s = seconds, ms = milliseconds, hr = hours, Pa = Pascals, MPa = megapascals, Pa·s = Pascal-second, mPa·s = millipascal-second, g / mol = grams per mole, g / e q = grams per equivalent, mg KOH / g = milligrams of potassium hydroxide per gram Grams, Mn = number-average molecular weight, Mw = weight-average molecular weight, pts = parts by weight, 1 / s or second - 1 = reciprocal of seconds [s -1 ], °C = Celsius temperature, mmHg = millimeters of mercury, psig = 1 pounds per square inch, kPa = kilopascals, % = percent, vol% = volume -cent, mol% = mole percent, and wt% = weight percent.

[0035] Unless otherwise specified, all percentages, parts, ratios, and other quantities are determined by weight. For example, all percentages described herein are subject to change unless otherwise indicated. It is a weight percentage (weight %).

[0036] Specific embodiments of the present invention are described below in this specification. These embodiments are described in this specification. The disclosure is detailed and complete and is provided to fully convey the scope of the subject matter of the invention to those skilled in the art. ru.

[0037] In general, the present invention relates to nylon compositions for various applications, particularly those with impact strength and flow properties. In applications requiring increased properties, when manufacturing nylon articles / products or parts... It includes reinforced polyamide (e.g., nylon) formulations or compositions that are useful for this purpose.

[0038] In broad embodiments, the reinforced polyamide composition of the present invention comprises (a) at least one poly an amide (e.g., a nylon compound), (b) at least one reinforcing agent component, and (c) strong To form a reinforced nylon composition so that the impact strength properties of the polyamide composition are improved. The blend or mixture includes at least one liquid low-viscosity siloxane polymer. .

[0039] Component (a), a polyamide compound of the nylon composition, is an essential part of the polymer backbone. The polymer contains repeating amide groups (R-CO-NH-R'). A polyamide compound useful in this invention may comprise one or more polyamide compounds. Suitable polyamide resins that can be used include any polyamide known in the art. Examples include aliphatic and semicrystalline polyamides. Examples include, but are not limited to, aromatic and semi-aromatic nylon resins, and mixtures thereof. Nylon resins are essentially lactam or diamine, aliphatic, semi-aromatic, or aromatic. It is prepared from dicarboxylic acids and mixtures thereof as starting materials. Suitable lactams that are useful include, for example, caprolactam, laurolactam, and Examples of mixtures of these include tetra Methylenediamine; Hexamethylenediamine (HMD); 2-Methylpentamethylene-di Amine; Undecamethylenediamine; Dodecamethylenediamine; 2.2.4-(2,4, 4-Trimethyl-hexamethylenediamine; 5-Methylnonaethylenediamine; Metaxy Relendiamine (MXD); paraxylylenediamine; 2-methyl-1,5-pentameth Examples include lenticamines (MPMDs) and mixtures thereof. These are useful in the present invention. Suitable dicarboxylic acids include, for example, adipic acid, suberic acid, azelaic acid, and sebacin. Acids, dodecane dioic acid (DDDA), terephthalic acid (TPA), isophthalic acid (IPA), 2 -Chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium Um-sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and These include mixtures of these.

[0040] In the present invention, nylon homopolymers or copolymers derived from these starting materials The polyamide resin is used either alone or in a mixture. Specific examples of fats include: (Nylon 6); Polyundecaneamide (Nylon 11); Polylauramide (Nylon 12); Polyhexamethylene adipamide ( Nylon 66); Polytetramethylene adipamide (Nylon 46); Polyhexamethylene Sebamid (Nylon 610); Polyhexamethylene Dodecamide (Nylon 612); Po Polyhexamethylene terephthalamide (6T); Polyhexamethylene isoterephthalamide (61); 2-methylpentamethylene terephthalamide (nylon DT); 2-methylpentamethylene Intamethylene isophthalamide (DI); polyhexamethylene terephthalamide / polycarbonate Plamid copolymer (nylon 6T / 6); polyhexamethylene terephthalamide / poly Dodecanamide copolymer (nylon 6T / 12); polyhexamethylene adipamide / Polyhexamethylene terephthalamide copolymer (nylon 66 / 6T); polyhexamethylene Lenadipamide / Polyhexamethylene isophthalamide copolymer (Nylon 66 / 61 ), polyhexamethylene adipamide / polyhexamethylene isophthalamide f-polycap Lamid copolymer (nylon 66 / 61 / 6); polyhexamethylene adipamide / polyhexamethylene Xamethylene terephthalamide / -polyhexamethylene isophthalamide copolymer ( Ilon 66 / 6T / 61); Polyhexamethylene terephthalamide / Polyhexamethylene Isophthalamide copolymer (nylon 6T / 61); polyhexamethylene terephthalamide Mid / Poly(2-methylpentamethylene)terephthalamide copolymer (Nylon 6T / M5T); Polyhexamethylene terephthalamide f-Polyhexamethylene sebacamido / Po Licapramidopolymer (Nylon 6T / 610 / 6); Polyhexamethylene Terephthalate Amide / Polydodecaneamide / Polyhexamethyleneadipamidopolymer (Nylon 6T / 12 / 66); Polyhexamethylene terephthalamide / Polydodecaneamide / -Polyhe Xamethylene isophthalamide copolymer (nylon 6T / 12 / 61); poly(m-xyl) Lylene adipamide (nylon MXD6); and any mixture and copolymer of the above compounds. Mar, etc.

[0041] In some preferred embodiments, component (a), which is a polyamide component, has an impact strength of It may be any desired polyamide. For example, the polyamide component may be (a) nylon- 6; (aii) Nylon-4,6; (aiii) Nylon-6,6; (aiv) Nylon -6,10; (av) Nylon-6,9 (avi) Nylon-6,12; (avii) Na Ilon-7; (aviii) Nylon 10; (aix) Nylon-10,10; (ax) Nylon-11; (axi) Nylon-12; (axii) Nylon-12.12; (a viii)6T~12T;(axiv)6I~12I;(axv)2-methylpentameth Didiamine and / or hexamethylenediamine, adipic acid, isophthalic acid and tereol Polyamides formed from one or more acids selected from the group consisting of phthalic acids; (axv i) Blends and / or copolymers of nylon and its polyamide; and (axv ii) A selection can be made from the group consisting of mixtures thereof.

[0042] In other preferred embodiments, the polyamide is nylon 6 (self-polymerizing caprolactam) Polycaprolactam made from, nylon 6,6 (repeated mesh within the polymer main chain) Hexamethylenediamine-adipic acid condensation product, a long-chain synthetic polyamide having a do group. ), nylon 4, nylon 11, nylon 6, 10; and groups consisting of combinations thereof. You can choose from these options.

[0043] In yet another preferred embodiment, a polyamide compound useful in the present invention is, Examples include ylon 6; nylon 6,6; and mixtures thereof.

[0044] In some embodiments, component (a), which is a polyamide component, is Ultramid sil You can choose from commercially available compounds such as BASF products. In embodiments, some examples of commercially available polyamide compounds useful in the present invention include: For example, Zytel 7304 NC010 (available from DuPont), PA6-Y H800(Yueyang Baling Shihua Chemical&Synt (Available from hetic Fiber Co. Ltd.), as well as mixtures thereof. It is possible.

[0045] The concentration of the polyamide component (a) is, in one embodiment, 50% to 98.99% by weight. Amount in %, in another embodiment 70% to 92% by weight, and in yet another embodiment 75% to 9% by weight. It can be 0% by weight.

[0046] A useful reinforcing component (b) (or impact resistance improving component) in the composition of the present invention is, for example, For example, maleic anhydride-grafted polyolefin elastomers; amine or carboxylic acid functionalities. Polyolefins; ionomers containing metal salts of carboxylic acid-functionalized polyolefins; and You can choose from those mixtures.

[0047] In some embodiments, component (b), which is a reinforcing agent component, is, for example, (bi) polymerized. Ethylene, polymerized α-olefins with at least one carbon atom between 3 and 12 carbon atoms, and branched chains, linear chains, and cyclic compounds having 4 to 14 carbon atoms. Essentially consisting of at least one polymerization unsaturated monomer selected from Lass A polymer; (bii) α,β ethylene polymer having 3 to 8 carbon atoms. Saturated dicarboxylic acids, and mono-alcohols having 1 to 29 carbon atoms. Neutralization with esters, anhydrides of dicarboxylic acids, metal salts of dicarboxylic acids, and metal ions Therefore, 0% to 100% of the aforementioned dika having ionized 0% to 100% carboxylic acid groups The induction selected from a class consisting of monoesters of the dicarboxylic acid having rubonic acid. (biii) an unsaturated monomer selected from the class consisting of conductors; and (biii) the above component (bi Selected from the group consisting of a mixture of (bii) and (b).

[0048] In some embodiments, a reinforcing agent component (also called an "impact-resistant modifier"; component (b) ) is a maleic anhydride-functionalized elastomer ethylene copolymer, maleic anhydride-functionalized e ethylene, α-olefin copolymer, ethylene, acrylic acid ester and maleic anhydride Terpolymer, maleic anhydride (MAH) grafted polyolefin elastomer (PO E) and combinations thereof. In one preferred embodiment, the reinforcing agent component is (b) is maleic anhydride grafted polyolefin elastomer (POE-g-MA H) is the answer.

[0049] In some embodiments, the reinforcing agent component is an Exxelor series product (ExxonM Available from obil; Tafmer series products (available from Mitsui Chemicals, Inc.) ; and commercially available compounds such as mixtures thereof can be selected, but are not limited to these. I can't.

[0050] Reinforcement component (b) is a mixture of the reinforcement component with nylon component (a) and PDMS component (c). Before that, the predetermined MAH graft rate, melt index, molecular weight, molecular weight distribution, and / or it can be further characterized as having branching. For example, the reinforcing agent component is In one embodiment, 0.1 to 5; in another embodiment, 0.2 to 2.0; and in yet another embodiment, 0 It has an MAH graft ratio of 0.3 to 1.0. For example, the impact resistance modifier is, in one embodiment, , 0.8g / cc to 0.95g / cc, in another embodiment, 0.83g / cc to 0.93 g / cc, and in yet another embodiment, having a density of 0.85 g / cc to 0.92 g / cc .

[0051] The reinforcing agent (impact resistance improver) compound used to prepare the nylon composition of the present invention The concentration of a certain component (b) is, for example, in one embodiment, based on the weight of the nylon composition, 1 In another embodiment, % to 50% by weight, in yet another embodiment, 8% to 35% by weight, and in yet another embodiment , containing 10% to 25% by weight.

[0052] In some embodiments, component (c), which is a siloxane-based component, is, for example, disin Roxane, trisiloxane, polydimethylsiloxane (PDMS), and mixtures thereof. These are some examples.

[0053] In one embodiment, the siloxane component is PDMS. Carbinol-functionalized PDMS This includes carboxyl-functionalized PDMS, amino-functionalized PDMS, and unfunctionalized PDMS. It has been found that the PDMS of this type is useful in the present invention, namely The selected type of PDMS mentioned above brings about a significant improvement in the impact strength of reinforced nylon. In some embodiments, PDMS is hydroxyl, amino, epoxy, carboxy Contains one or more functional groups such as sil, mercapto groups, or mixtures thereof, including carbon groups. This is also fine. In some embodiments, the functional group in polydimethylsiloxane is polydimethylsiloxane. Located at the end of the siloxane chain or on the side of the polydimethylsiloxane chain. Useful in the present invention A suitable example of non-functionalized PDMS is The DOW Chemical Company. One or more XIAMETER(trademark) PMX-200 series products manufactured in NY are listed. It can be done.

[0054] PDMS with different molecular weights (Mw; determined by viscosity) are reinforced nylon compounds. It has also been found to improve the impact strength of the product. Amino-functionalized PDMS also It offers further advantages related to fluidity, such as reduced capillary viscosity.

[0055] In some embodiments, the siloxane component (PDMS) used in the present invention is XI AMETER(TM) PMX-200(The Dow Chemical Compa Available from NY); KF series products (available from SHIN-ETSU Co.Ltd.) Possible); and can be selected from commercially available compounds such as mixtures thereof. One embodiment In this invention, a useful non-functionalized PDMS is The Dow Chemic Examples include commercially available products from al Company. In another embodiment, the present invention Functionalized PDMS useful in this context is available from SHIN-ETSU Co.Ltd. It is a commercially available product. However, PDMS is not limited to solid or pelletized versions. It is used in liquid form.

[0056] In some embodiments, the viscosity of the siloxane-based component is, in a general embodiment, 1 mm 2 / s to 100,000 mm 2 / s, in another embodiment 3 mm 2 / s to 90,000 mm 2 / s, and in yet another embodiment 5 mm 2 / s to 80,000 mm 2 / s and may be.

[0057] The concentration of component (c) which is a siloxane-based component is, in one embodiment, based on the nylon composition and is 0.01% to 10% by weight, in another embodiment 0.1% to 8% by weight, and in yet another embodiment it may be 0.2% to 5% by weight.

[0058] In some embodiments, the reinforced polyamide composition of the present invention can further contain, if desired, one or more optional components, additives or other pharmaceutical compounds. Component (d) which is an optional compound useful in the reinforced polyamide composition of the present invention includes, for example, fillers, lubricants, plasticizers, pigments, dyes, antioxidants, stabilizers, nucleating agents, flame retardants, foaming agents, and mixtures thereof. And can be mentioned.

[0059] Generally, the concentration of the optional compound, when used in the reinforced polyamide composition, is, for example, in one embodiment 0% to 50% by weight, in another embodiment 0.01% to 50% by weight, and in yet another embodiment 0.1% to 40% by weight, and in still another embodiment 0.1% by weight to 30% by weight.

[0060] In a general embodiment, the reinforced nylon composition comprises (a) at least one polyamide (for example, a nylon compound), (b) at least one reinforcing agent component, and (c) 1 mm2 / s~100,000mm 2 At least one liquid low viscosity siloxane having a viscosity of / s It can be manufactured by combining, blending, or mixing polymer systems. The resulting mixture forms a reinforced nylon composition exhibiting improved impact strength properties. .

[0061] An example of one embodiment of the present invention, without limitation, is the reinforced nylon of the present invention. A general method for producing the composition is (a) based on the weight of the reinforced nylon composition, 5 (b) a polyamide at least one in a concentration of 0% to 98.99% by weight, and (b) reinforced nylon Based on the weight of the composition, at least one reinforcing agent in a concentration of 1% to 50% by weight, ( c) Based on the weight of the reinforced nylon composition, a concentration of at least 0.01% to 10% by weight (d) an additional siloxane polymer and, if necessary, based on the weight of the reinforced nylon composition. Then, mix, combine, or This includes blending.

[0062] In some embodiments, to prepare a reinforced polyamide composition exhibiting improved toughness The present invention provides a method in one step, at a predetermined temperature and for a predetermined time, that involves a polyamide component (a), a reinforcing agent component (b), and a siloxane polymer component (c) are dissolved This includes melting and mixing. One melting and mixing step is performed at a temperature of 200°C or higher in one embodiment, and in another embodiment In one embodiment, the temperature range is 200°C to 350°C, in another embodiment, it is 220°C to 320°C, and in yet another embodiment... In this state, the process can be carried out at a melting temperature of 250°C to 300°C. Time for one melting and mixing step In one embodiment, this is more than 20 seconds; in another embodiment, it is 20 seconds to 10 minutes; and in yet another embodiment, it is more than 20 seconds. This can range from 30 seconds to 5 minutes. In one embodiment, the above one-step melting and mixing method is a conventional twin-axis method. This is done using at least one extruder, such as a screw extruder (with at least two screws). It is possible.

[0063] In other embodiments, for preparing a reinforced polyamide composition exhibiting high fluidity and toughness The method of the present invention includes at least the following two steps: (I) at least The following two components: (α)POE-g-MAH and other reinforcing agent components (b); and (β)P The above siloxane-based polymer component (c), such as DMS, is subjected to a predetermined temperature and time. Mix to form a blended composite component (i.e., reinforcing agent / siloxane polymer mixture) (II) (γ) the polyamide component (a) and (δ) The blended composite components from step (I) are melted and mixed to form a reinforced polyamide composition. The second step.

[0064] The first mixing step (I) involves, for example, immersing or blending components (b) and (c) together, and then For example, components immersed or compounded using at least one twin-screw extruder. This can be done by mixing. When using the immersion method in the first mixing step (I) In addition, the temperature of the first mixing step (I) is less than 60°C in one embodiment and 0°C in another embodiment. ~60°C, and in yet another embodiment, it may be 10°C to 55°C. When using the immersion method, The time for mixing step (I) is more than 1 hour in one embodiment, and 1 to 48 hours in another embodiment. The duration can range from 2 to 24 hours in yet another embodiment.

[0065] When a compounding method is used in the first melting and mixing step (I), the first melting and mixing step (I) is In one embodiment, the temperature is over 100°C; in another embodiment, it is between 100°C and 200°C; and in yet another embodiment, it is between 100°C and 200°C. This can be carried out at a temperature of 120°C to 180°C. When using a compounding method, the first mixing step (I) The time is more than 1 second in one embodiment, 20 seconds to 10 minutes in another embodiment, and yet another embodiment Depending on the application method, the duration can range from 30 seconds to 5 minutes.

[0066] When using the immersion method in the first mixing step (I), the temperature of the second melt-dissolve mixing step (II) In one embodiment, the temperature exceeds 200°C, in another embodiment, it is 230°C to 350°C, and in yet another embodiment... The temperature can be between 250°C and 300°C. The duration of the second step (II) of melting and mixing is one implementation. In one embodiment, it is more than 1 second; in another embodiment, it is 20 seconds to 10 minutes; and in yet another embodiment, it is 30 seconds to 5 minutes. This is possible. In one embodiment, the second step (II) of melt mixing described above is performed using a conventional twin-screw screwdriver. This should be done using at least one extruder, such as a leu (at least two-screw) extruder. It is possible.

[0067] When a compounding method is used in the first mixing step (I), the melting and mixing step (II) is the first mixing This process can be carried out at the same temperature and time as the combination process (I).

[0068] In other embodiments, a method for preparing a reinforced polyamide composition exhibiting high toughness is described as follows: It can include at least the following three steps: (A) at least the following two components: ( α) at ​​least one reinforcing agent component (b), e.g., POE-g-MAH; and (β) Dissolve at least one siloxane-based component, such as a siloxane-based polymer like PDMS. Step (B) is to melt and mix to form a reinforcing agent / siloxane polymer mixture. A) Reinforcement agent / siloxane polymer mixture is pelletized into multiple composite pellets A second step of forming (C) at least two components: (γ) at least one (ε) Polyamide; and multiple composite pellets from step (B) are melt-mixed to reinforce the polyamide. A third step in forming the riamid composition. In one embodiment, the third step is the melt mixing described above. C) A conventional twin-screw (at least two-screw) extruder, etc. This can be done with a single extruder.

[0069] The temperature of the first step (A) of melt mixing is less than 200°C in one embodiment, and in another embodiment The temperature can be 100°C to 200°C, and in yet another embodiment, 120°C to 180°C. The time for mixing in step (A) is more than 1 second in one embodiment and 20 seconds in another embodiment. This can range from seconds to 10 minutes, and in yet another embodiment, from 30 seconds to 5 minutes.

[0070] The pelletizing process (B) cuts the resin coming out of the extruder into pellets of a predetermined size. This is done using conventional equipment such as strand cutters.

[0071] The temperature of the third step (C) of melt mixing is, in one embodiment, above 200°C, in another embodiment... This can be a temperature of 230°C to 350°C, and in yet another embodiment, 250°C to 300°C. The time for the third step (C) of melt mixing is more than 1 second in one embodiment and 20 seconds in another embodiment. This can range from seconds to 10 minutes, and in yet another embodiment, from 30 seconds to 5 minutes.

[0072] Embodiments of the method of the present invention for preparing a reinforced polyamide composition, and the above-mentioned This process can be carried out by conventional apparatus known to those skilled in the art. For example, uniform or homogeneous The mixing of components to form a mixture is done using a twin-screw extruder, a BUSS kneader, and a BUSS. This can be done using a known blender or mixer, such as a Chimixer.

[0073] As described above, the reinforced polyamide composition of the present invention comprises (a) at least one polyamide (e.g., a nylon compound) and (b) at least one reinforcing agent component (e.g., POE- g-MAH) and (c) 1 mm 2 / s~100,000mm 2 Having a viscosity of less than / s This also includes a mixture with one liquid low-viscosity siloxane polymer (e.g., PDMS). The reinforced polyamide composition of the invention exhibits several advantageous features. For example, the polyamide is P When mixed with OE-g-MAH and PDMS, the resulting reinforced polyamide composition is The benefit is enhanced impact strength at room temperature. In addition, depending on the circumstances, the reinforced polyamide of the present invention The fluidity of the composition (nylon composition) can also be improved. Therefore, at least One nylon, at least one POE-g-MAH and at least one PDMS The combination forms the reinforced polyamide composition of the present invention having at least increased impact strength. In addition, the impact properties of the reinforced polyamide composition of the present invention are similar to those of the reinforced nylon composition. When polyamide is blended with POE-g-MAH and PDMS to achieve bending, Other mechanical properties of reinforced nylon composition, such as elastic modulus, tensile strength, elongation, and heat distortion temperature (HDT). Performance can be improved while maintaining an optimized level.

[0074] For example, in one common embodiment, a reinforcing agent component (e.g., POE-g-MAH) and Reinforced polyamide compositions containing roxane-based polymers (e.g., PDMS) are advantageous in that The present invention contains a reinforcing agent component (e.g., POE-g-MAH), but is a siloxane polymer. Compared to nylon compositions that do not contain (e.g., PDMS), at room temperature (RT) or -3 It shows at least a 10% improvement (e.g., increase) in impact strength at temperatures below 0°C. Another implementation In form, the reinforced polyamide composition of the present invention includes the above-mentioned reinforcing agent component and siloxane-based polymer. The material contains the above-mentioned reinforcing agent components but does not contain the siloxane-based polymer of the present invention. Compared to the original composition, it showed at least a 15% improvement in impact strength; further implementations In this state, the reinforced polyamide of the present invention contains the above-mentioned reinforcing agent component and the siloxane-based polymer of the present invention. The composition contains the above-mentioned reinforcing agent component but does not contain the siloxane polymer of the present invention. Compared to the riamid composition, it shows at least a 20% improvement in impact strength. In the embodiment, the reinforcing polymer of the present invention comprises the above reinforcing agent component and the siloxane polymer of the present invention. The riamide composition contains the above-mentioned reinforcing agent component, but also contains the siloxane polymer of the present invention. Compared to polyamide compositions without this component, it shows a 10% to 100% improvement in impact strength.

[0075] Surprisingly, the above-mentioned RT / low-temperature impact strength of the reinforced polyamide composition of the present invention is The improvement involves adding only a small amount (e.g., less than 5% by weight) of PDMS to the reinforced nylon composition. It was found that this can be achieved by low filler (e.g., reinforced polya Based on the total weight of the midi formulation, 0.4% to 2% by weight of PDMS is POE-gM Along with AH, high filling volume is required, for example, by compositions known in the art. Compared to 20% to 80% by weight PDMS, the RT / of the reinforced polyamide composition of the present invention To form an impact resistance modifier that is effective in improving low-temperature impact strength. Also, using conventional technology The molecular weight of the PDMS used in this invention is the molecular weight of the PDMS (by measuring viscosity). (determined by) greater than. In the present invention, the reinforced polyamide composition is a specific molecule It does not require a large amount of PDMS. However, in one preferred embodiment, the composition of the present invention To improve impact strength, 1mm 2 / s~100,000mm 2 Measurement viscosity in the range of / s A PDMS with a certain degree of accuracy is desirable.

[0076] Another advantage of the nylon composition of the present invention is that it maintains impact strength while maintaining the flexural modulus of the composition. To have the above-mentioned improved properties (e.g., at RT and low temperatures), it has a thinner wall. Nylon composition for manufacturing lightweight articles / products or parts using less composition The ability to use it.

[0077] Articles / products or parts manufactured from the reinforced nylon composition of the present invention are, for example, electronic devices. This may include automotive parts, gears, and toys.

[0078] Components of the reinforced nylon composition of the present invention: (a) at least one polyamide (e.g., na (b) an iron compound, (b) at least one reinforcing agent component, and (c) at least one sil When xane polymers are completely and uniformly mixed, for example at the melt mixing temperature, the resulting melt Using a mixture, articles / products or molded parts can be formed using conventional methods and apparatus. This can be done. For example, using methods such as injection molding, extrusion molding, or blow molding, Articles / products or molded parts can be formed from reinforced nylon compositions.

[0079] In one preferred embodiment, the article / product or molded part is, for example, an injection molding method and It is produced and processed using extrusion equipment such as a twin-screw extruder. Generally, the present invention A method for producing an article from a reinforced polyamide composition is, for example, (1) the above-mentioned reinforced polyamide Using any one of the methods for producing the composition, (a) at least one polyamide, (b) at least one reinforcing agent component, and (c) at least one siloxane polymer. (1) A step of providing a reinforced polyamide composition by mixing (2) the combination of (1) The process involves processing the material into an article using, for example, an extrusion method or an injection method to form an article. , including.

[0080] To create thinner and therefore lighter parts, nylon compositions must have high impact strength It is necessary to have a degree. The nylon composition of the present invention has a composition such as flexural modulus, in addition to other properties. While maintaining the properties, the reinforced nylon composition of the present invention is created by using appropriate components (a) to (c). By forming a material, it is possible to demonstrate an improvement in impact strength (or toughness). Such high-performance properties of the nylon composition are due to the superior performance of the nylon composition produced from the reinforced nylon composition of the present invention. This enables downgauging of interior and exterior components and articles that require specific impact characteristics. do.

[0081] Impact-resistant additive, reinforced nylon composition, and manufactured from the above-mentioned reinforced nylon composition. The manufactured articles, products, or components are intended for use in a wide range of polymer compositions and structures. This is possible. Generally, the reinforced nylon composition of the present invention is a part made from a conventional copolymer. A component with higher impact strength (i.e., increased toughness and durability) than the product is required. It is used in a certain application. For example, but is not limited to, reinforced nylon composition. It can be used for a variety of applications and is useful in fields requiring impact resistance and strength. It can be formed into a molded product. In one embodiment, for example, the reinforced nylon composition is It can be used in automotive applications to manufacture rigid parts and components for motor vehicles. Automotive products can be manufactured using conventional polymer processing methods. [Examples]

[0082] The following are examples (Inv.Ex.) and comparative examples (Comp.Ex.) of the present invention (collectively) Examples (referred to as "Examples") are presented herein to further illustrate the features of the present invention. However, it is intended to be interpreted, both explicitly and implicitly, as limiting the scope of the patent claims. No. Examples of the present invention are identified by Arabic numerals, and comparative examples by alphabetical letters. Thus, it is represented. The performance of the embodiments of the compositions described herein was analyzed in the following experiments. Unless otherwise specified, all parts and percentages are based on total weight.

[0083] raw materials The raw materials (components) used in the examples to prepare the reinforced nylon composite material formulation were PA 6 B3s, polyamide nylon (available from BASF); and POE-g-MAH 1 (0.50 wt% MAH graft level) and POE-g-MAH2 (0.90 wt% Contains MAH graft level, maleic anhydride grafted polyolefin elastomer It was measured according to ASTM D1238 at 190°C with a load of 2.16 kg. Thus, POE-g-MAH1 has a melt index (MI) of 1.6g / 10min. Furthermore, POE-g-MAH2 had an MI of 1.3 g / 10 min. The PDMS materials are listed in Table I.

[0084] [Table 1]

[0085] compound The reinforced nylon composite material formulations used in the examples are shown in Table II for the Series 1 experiments. Furthermore, the experiments for Series 2 were prepared based on the formulations listed in Tables IV and V. did.

[0086] [Table 2] Notes on Table II: * The amount of PDMS is based on the total weight of the nylon composition.

[0087] [Table 3] Notes on Table III: * The amount of PDMS is based on the total weight of the nylon composition.

[0088] [Table 4] Notes to Table IV: * The amount of PDMS is based on the total weight of the nylon composition.

[0089] [Table 5] Notes on Table V: * The amount of PDMS is based on the total weight of the nylon composition.

[0090] Generally, the reinforced nylon composite materials listed in Tables II-V contain P as the PDMS component. The first step is to blend the OE component with the PDMS / POE component, followed by the blended PDMS / POE component. It was prepared by a second step of mixing it with the ron component.

[0091] The first step of blending the PDMS component with the POE component is described below in this specification. This is done by utilizing either an immersion procedure or a compounding procedure.

[0092] Immersion method for blending PDMS with POE PDMS containing PDMS of KF-6000 (Examples 1-3 and Examples of the present invention) 21) KF-6001 (Examples 4 and 5 of the present invention); KF-8010 (Example of the present invention) 6 and 7); X-22-161A (Examples 8 and 9 of the present invention); X-22-162C (This Examples 10 and 11 of the Invention); PMX-200 fluid 10 cSt (Examples 12-1 of the Invention) 4 and Example 22 of the present invention), PMX-200 fluid 20 cSt (Examples 15-1 of the present invention) 6 and Examples 23 and 24 of the present invention, and PMX-200 fluid 100 cSt (present invention) Examples 17 and 25 of the present invention were blended with POE pellets by immersion method. First, PDMS was mixed with POE at room temperature, and then the PDMS was added to the body of the POE pellet. It was soaked, or rather, permeated. 400g of POE pellets were first soaked in 2L of plastic. Place in a container, then add PDMS according to the weight percentages in Tables II and III. It was added to the container containing the mixture of POE pellets and PDMS, in different directions (similar Shake the container by hand (up and down and left and right) for 5 minutes. Stop shaking, lay the container on its side, and let it sit for 5 minutes. The mixture was left to stand. After repeating the shaking and tilting of the container six times, it was kept at room temperature for a further three hours. Alternatively, premix the PDMS with POE at room temperature, then place it in an automatic shaker, and then... It can be shaken at 60°C and 85 rpm for 4 to 12 hours.

[0093] Formulating method for blending PDMS with POE PMX-200 Fluid 1K cSt PDMS (Example 18 of the present invention, and implementation of the present invention) Examples 26 and 27) include PDMS; PMX-200 fluid 1K cSt (15%) (Invention) Examples 28-30); PMX-200 fluid 10K cSt (Example 19 of the present invention); P MX-200 fluid 60k cSt (Example 20 of the present invention); and DOWSIL (trademark) S GM 15 GUM (Comparative Examples B and C) were each compounded using a twin-screw extruder method. Then it was blended with POE pellets. Before feeding the blend into the extruder, the PDMS was first It was blended with POE, and then the blend was fed into an extruder. The extruder used was as follows: It had the following conditions / parameters:

[0094] The equipment used was a ZSK-18 twin-screw extruder; the extruder's output was 19. The power output is 2KW; the diameter of the extruder D is D=18mm; and the L / D ratio of the extruder is L / D= The temperature was set to 48; the temperature of various zones in the extruder barrel was set as follows: RT~150 Within the range of °C, Zone 1 = 60°C, Zone 2 = 90°C, Zone 3 = 120°C, Zone Zone 4 = 120°C, Zone 5 = 120°C, Zone 6 = 120°C, and Zone 7 = 110°C; press The screw speed of the extruder is 300 rpm, and the feed rate of the blend material to the extruder is 5~ The rate was 12 kg / hour.

[0095] After the blending process of PDMS and POE in a twin-screw extruder, the obtained PDMS A blend of POE compounds, with a diameter of 0.5mm to 1mm and a length of 2mm to 5mm. It was cut into pellets.

[0096] Formulation of PDMS / POE mixture into nylon The nylon sample was first dried in a dehumidifier at 120°C for at least 4 hours. Then, as described above... Method: "Immersion method for blending PDMS with POE" or "Deep PDMS with POE and Blended PDMS / POE pellets manufactured using the "Formulation Method for Blending" The PDMS / POE pellets and nylon sample are mixed in an extruder and then dried. It was blended with a nylon sample. The extruder used was P It was the same extruder used to blend DMS with POE. PDMS / PO The extruder conditions / parameters for compounding E pellets and nylon samples are as follows: As expected: The extruder barrel temperature was set in the range of RT ~ approximately 350°C as follows: Settings: Zone 1 = 150°C, Zone 2 = 195°C, Zone 3 = 260°C, Zone 4 = 260°C, Zone 5 = 260°C, Zone 6 = 260°C, Zone 7 = 250°C; Extruder The clew speed is 250 rpm, and the feed rate of the blend material to the extruder is 8-10 kg. It was [time].

[0097] After mixing PDMS / POE pellets and nylon samples, PDMS, POE and nylon The resulting mixture, including the Ron blend, is divided into diameters of 0.5mm to 1mm and 2mm to 5mm. It was cut into pellets of a certain length.

[0098] Test method The following test methods and measurement procedures were used to test the reinforced nylon composition and, according to the following method, Test specimens prepared from reinforced nylon compositions were tested.

[0099] Capillary viscosity test The formulated nylon / POE sample was first placed in a dehumidifier at 120°C for at least 4 hours. After drying the compounded sample, the compounded sample is then subjected to aluminum foil under vacuum. Sealed inside the bag. 874 Oven Sample Processor (Therm (Available from o-Fisher Co. Ltd.) Using the so-called Carl Fuss The moisture content in the blended nylon / POE samples was tested using the char method. The moisture content of the Ron / POE sample should be 1,000 pp before testing the sample using a capillary viscosity test. It is recommended that the value be less than m. The capillary rheometer instrument used for the capillary viscosity test was: Gottfert rheograph 26 (available from Gottfert Inc.) The result was (capacitance). The test temperature used for the capillary viscosity test was 260°C. The length was 30 mm and the diameter of the capillary tube was 1 mm. The shear rate used in the test was 90 The viscosity ranged from 1 / s to 7,000 1 / s. The data listed in the viscosity table is as follows: This is reported at a shear rate of 770 1 / s.

[0100] Injection molding method The mixed nylon / POE pellets were first dehumidified at 120°C for at least 4 hours. After drying, the pellets were subjected to injection molding. Injection molding machine: Fanuc Robosho The t S-2000i100BH (available from Fanuc) was used for the injection molding method. The compounded sample is subjected to injection molding to produce a test specimen, as described below in this specification. Impact tests were performed on the test specimens using an impact strength test. The parameters of the injection molding machine and method were also measured. The procedure was as follows: The barrel temperature of the injection screw was set to 250°C to 260°C. The cooling temperature was 190°C, the cooling time was 15 seconds, and the injection speed was 30 mm / second. The injection pressure was 200 MPa.

[0101] Impact strength test The impact strength test method used to test the impact performance of the test specimens prepared in the examples was C HARPY, ISO 179 ("ISO" stands for "International Organization for Standardization") It is stated in the document "on for Standardization". CHARPY, ISO179 is To identify a method for determining the Charpy impact strength of plastics under defined conditions. The test specimens used in this test are prepared from the formulations listed in Tables II to V, and have the following dimensions. : A flat test specimen measuring 80 mm in length, 10 mm in width, and 4 mm in thickness. CHARPY, ISO 179 uses a pendulum system with appropriately sized hammer arms. Therefore, to determine the plastic's resistance to fracture when subjected to impact in a three-point bending configuration... This defines the method used for the test. The test does not use any equipment and is necessary to destroy the test specimen. Used to determine energy. Different test parameters are used when the test specimen is prepared. It is determined according to the type of material used and the type of notch cut in the test specimen being tested. .

[0102] In the embodiments described herein, the following general procedure was followed: All test specimens were subjected to a radius of 2 A notch of mm was made. Before testing the specimens, all specimens were first dried in a dehumidifier at 12

[0103] Each specimen to be tested was horizontally attached to a pendulum impact tester and supported without fixing both ends. The hammer of the tester was released to penetrate the specimen. If no damage occurred with the first hammer arm used, heavier hammers were sequentially used until damage occurred. Then, at the time of breakage, the energy obtained and the type of fracture were recorded.

[0104] The impact test conditions used were as follows: pendulum capacity of 4 joules and specimen conditioning at room temperature for ≥ 6 hours or in a freezer at -30 °C and / or -40 °C for ≥ 6 hours. The specimens in the freezer were taken out of the freezer and the impact test was carried out within 5 seconds. The test conditions were room temperature (i.e., a temperature of 23 °C ± 2 °C) and 50% RH ± 10% RH.

[0105] Test Results The viscosity results of the reinforced nylon formulations were obtained by conducting the capillary viscosity test described above; the viscosity results for the Series 1 experiments are described in Table VI; the viscosity results for the Series 2 experiments are described in Table VII. The results of the normalized capillary viscosity were calculated by dividing the capillary viscosity value of the sample by the capillary viscosity value of a specific comparative example shown in the column headings of the following table, and then multiplying that value by 100 to convert it to a percentage. The results of the normalized Izod impact were also calculated by dividing the Izod impact value of the sample by the Izod impact value of a specific comparative example (as shown in the headings of the following table), <00009​​​​​​​​​​​​

[0106] [Table 6] Notes to Table VI: (1) Lower viscosity is preferable and desirable.

[0107] [Table 7] Notes to Table VII: (1) Lower viscosity is preferable and desirable.

[0108] The impact strength results of injection-molded test specimens made from reinforced nylon compound are as follows: By performing the above impact strength test on injection-molded test specimens prepared according to the shaping method, The results were obtained. The impact strength results from Series 1 experiments are shown in Table VIII, and the results from Series 2 experiments are shown. The impact strength results are recorded in Table IX.

[0109] [Table 8] Notes to Table VIII: (1) Is a higher flexural modulus value better compared to the control? or not significantly decreased; these values ​​are desirable.

[0110] [Table 9]

[0111] Analysis of the results In the Series 1 experiment, different types of PDMS (carbinol, amino, carboxy) were used. (Both functionalized and non-functionalized) samples were immersed in POE-g-MAH1 with different amounts of PDMS added. Next, the PDMS-soaked POE is treated with PA6 B3s (a medium viscosity POE available from BASF). It was blended with reamid nylon (nylon 6). The capillary viscosity characteristics of the blends in Series 1 experiments are described in Table VI, and the impact strength characteristics of the test pieces produced from the blends are described in Table VIII. When the reinforced polyamide composition of the present invention is compared with a control blend, for example, reinforced polyamide nylon PA6 B3s reinforced with the reinforcing agent POE-g-MAH1, all of the examples of the present invention showed a remarkable improvement in the room temperature impact strength characteristics of the reinforced polyamide composition containing PDMS. Samples of the reinforced polyamide composition of the present invention reinforced with POE and containing a PDMS additive also showed a remarkable improvement in the impact strength characteristics at a low temperature of -30°C. In addition,

[0112] the examples of the present invention showed flexural modulus performance maintained or improved with respect to the comparative examples. The results support the conclusion that the PDMS additive can significantly improve the reinforcing efficiency of POE. Furthermore, there is no significant difference in the impact strength regardless of whether the PDMS is functionalized or not. Also, the viscosity of PDMS (correlated with the molecular weight) showed no significant difference in the impact strength at room temperature for the reinforced polyamide composition, however, higher viscosity PDMS (correlated with higher molecular weight PDMS) showed less improvement in the impact strength at -30°C for the reinforced polyamide composition. For example, the -30°C impact strength of the reinforced polyamide composition containing PDMS, PMX-200 fluid 10 cSt to PMX-200 fluid 100 cSt (Examples 12 to 17 of the present invention) was compared with the reinforced polyamide composition containing PDMS, PMX-200 fluid 1 k cSt and PMX-200 fluid 10 k cSt. The results support the conclusion that the PDMS additive can significantly improve the reinforcing efficiency of POE. Furthermore, there is no significant difference in the impact strength regardless of whether the PDMS is functionalized or not. Also, the viscosity of PDMS (correlated with the molecular weight) showed no significant difference in the impact strength at room temperature for the reinforced polyamide composition, however, higher viscosity PDMS (correlated with higher molecular weight PDMS) showed less improvement in the impact strength at -30°C for the reinforced polyamide composition. For example, the -30°C impact strength of the reinforced polyamide composition containing PDMS, PMX-200 fluid 10 cSt to PMX-200 fluid 100 cSt (Examples 12 to 17 of the present invention)

[0113] The results support the conclusion that the PDMS additive can significantly improve the reinforcing efficiency of POE. Furthermore, there is no significant difference in the impact strength regardless of whether the PDMS is functionalized or not. Also, the viscosity of PDMS (correlated with the molecular weight) showed no significant difference in the impact strength at room temperature for the reinforced polyamide composition, however, higher viscosity PDMS (correlated with higher molecular weight PDMS) showed less improvement in the impact strength at -30°C for the reinforced polyamide composition. For example, the -30°C impact strength of the reinforced polyamide composition containing PDMS, PMX-200 fluid 10 cSt to PMX-200 fluid 100 cSt (Examples 12 to 17 of the present invention) was compared with the reinforced polyamide composition containing PDMS, PMX-200 fluid 1 k cSt and PMX-200 fluid 10 k cSt. The results support the conclusion that the PDMS additive can significantly improve the reinforcing efficiency of POE. Furthermore, there is no significant difference in the impact strength regardless of whether the PDMS is functionalized or not. Also, the viscosity of PDMS (correlated with the molecular weight) showed no significant difference in the impact strength at room temperature for the reinforced polyamide composition, however, higher viscosity PDMS (correlated with higher molecular weight PDMS) showed less improvement in the impact strength at -30°C for the reinforced polyamide composition. For example, the -30°C impact strength of the reinforced polyamide composition containing PDMS, PMX-200 fluid 10 cSt to PMX-200 fluid 100 cSt (Examples 12 to 17 of the present invention) was compared with the reinforced polyamide composition containing PDMS, PMX-200 fluid 1 k cSt and PMX-200 fluid 10 k cSt. The results support the conclusion that the PDMS additive can significantly improve the reinforcing efficiency of POE. Furthermore, there is no significant difference in the impact strength regardless of whether the PDMS is functionalized or not. Also, the viscosity of PDMS (correlated with the molecular weight) showed no significant difference in the impact strength at room temperature for the reinforced polyamide composition, however, higher viscosity PDMS (correlated with higher molecular weight PDMS) showed less improvement in the impact strength at -30°C for the reinforced polyamide composition. For example, the -30°C impact strength of the reinforced polyamide composition containing PDMS, PMX-200 fluid 10 cSt to PMX-200 fluid 100 cSt (Examples 12 to 17 of the present invention) was compared with the reinforced polyamide composition containing PDMS, PMX-200 fluid 1 k cSt and PMX-200 fluid 10 k cSt. Comparing the -30°C impact strength of (Examples 18 and 19 of the present invention), the higher viscosity PM X-200 fluid PDMS (meaning PMX-200 fluid PDMS with a higher Mw) It has a much smaller improvement in the impact strength of reinforced polyamide compositions at -30°C. In experiment 1, PMX-200 fluid 1k cSt and PMX-PMX-200 fluid Since 10k cSt PDMS has high Mw characteristics, these two PDMS samples Please note that these two PDMS samples cannot be immersed in POE. First, instead of the immersion method, a compounding method was used to mix the POE with the POE at 100°C.

[0114] In addition to impact strength, amino and carboxyl PDMS exhibited a significant decrease in capillary viscosity. Tables VI and VII show the PDMS at 770°S (typical shear for capillary viscosity testing). The capillary viscosity is described. The results show that a decrease of approximately 30% in the viscosity of PDMS occurs. Amines or organic acids can improve the fluidity of reinforced nylon compositions.

[0115] In the Series 2 experiment, various PDMSs were used with different PDMS loadings. It was mixed with Eg-MAH2. The capillary viscosity characteristics of the formulation in Series 2 experiments are shown in Table VI. The impact strength characteristics of the test specimens prepared from the compound are described in I and shown in Table IX. The results for IX show the same improvement in impact strength at room temperature and -30°C. When formulations with a 5% POE filling amount were also tested, the same improvement trend was observed. Too high. For formulations containing PDMS (e.g., 10% PDMS in POE), the results were as follows: Compared to formulations containing 2% to 5% PDMS, it showed a decrease in impact strength at room temperature. Unexpectedly, the results regarding the amount of PDMS added to the reinforced polyamide composition did not affect the improvement in impact strength. This may have an impact, and therefore, to provide the desired impact strength of the reinforced polyamide composition. Therefore, it was found that appropriate selection of PDMS filling amount is necessary.

Claims

1. A reinforced polyamide composition, (a) at least one polyamide, (b) at least one reinforcing agent component, (c) A 1 mm reinforced polyamide composition to provide a reinforced polyamide composition having increased impact strength. ２ / s~100,000mm ２ A siloxane-based component having a viscosity of / s, Includes reinforced polyamide composition.

2. The functionalized polar terminal group in at least one siloxane-based component is a hydroxyl group; Claims comprising mino groups; epoxy groups; carbonyl groups; mercapto groups, and mixtures thereof. The reinforced polyamide composition described in 1.

3. The non-functionalized nonpolar terminal group in at least one siloxane-based component is an allyl group; A reinforced polyamide composition according to claim 1, comprising kill groups and mixtures thereof.

4. The concentration of component (a), which is at least one polyamide, is equal to the composition of the reinforced polyamide. Based on the total weight of the object, it is 50% by weight to 98.99% by weight, and the at least one of the above strengths The concentration of component (b), which is a chemical agent component, is 1% by weight to 50% by weight, and at least one of the above The strong Polyamide composition.

5. The polyamide component (a) is (ai) nylon-4,6; (aii) nylon -6,6; (aiii) Nylon-6,10; (aiv) Nylon-6,9; (av) Na Ilon-6,12(avi) Nylon-11;(avii) Nylon-12;(avii i) 6T to 12T; (aix) 6I to 12I; (ax) 2-methylpentamethylenediamine n and / or hexamethylenediamine, and adipic acid, isophthalic acid and terephthalic acid Polyamides formed from one or more acids selected from the group; and (axi) pre Selected from the group consisting of nylon and its polyamide blends and / or copolymers. The reinforced polyamide composition according to claim 1.

6. The reinforced polyamide composition does not contain the at least one siloxane component. Compared to the riamid composition, it shows an increase of at least 10 percent in impact strength. The reinforced polyamide composition according to claim 1.

7. The composition may be enriched with up to 50% by weight of fillers, lubricants, Plasticizers, pigments, dyes, antioxidants, stabilizers, nucleating agents, flame retardants, blowing agents, and combinations thereof. The reinforced polyamide composition according to claim 1, comprising a component selected from the group consisting of combinations.

8. A method for preparing a reinforced polyamide composition exhibiting high fluidity and toughness, (a) at least one polyamide, (b) at least one reinforcing agent component, (c) A 1 mm reinforced polyamide composition to provide a reinforced polyamide composition having increased impact strength. ２ / s~100,000mm ２ A siloxane-based component having a viscosity of / s, The process involves melting and mixing components (a) to (c) in one step at a predetermined temperature and for a predetermined time. A method wherein the melting and mixing of the above is carried out at a temperature exceeding 200°C.

9. A method for preparing a reinforced polyamide composition exhibiting high fluidity and toughness, (I) At a temperature below 60°C, the following two components: (α) at ​​least one reinforcing agent component, (β) Mixing with at least one siloxane-based component to form a blended composite component The process to be completed, (II) At temperatures above 200°C, the following two components: (γ) at least one polyamide, (ε) The blended composite material components from step (I) are melted and mixed to increase the impact A method comprising the step of forming a reinforced polyamide composition having strength.

10. A method for preparing a reinforced polyamide composition exhibiting high fluidity and toughness, (A) At temperatures above 100°C, the following two components: (α) at ​​least one reinforcing agent component, (β) A blended composite material component obtained by melting and mixing at least one siloxane-based component. The process of forming, (B) The blended composite material components from step (A) are pelletized into multiple composite material pellets The process of forming a net, (C) At temperatures above 200°C, the following two components: (γ) at least one polyamide, (ε) The multiple composite material pellets from step (B) are melted and mixed to increase the impact A method comprising the step of forming a reinforced polyamide composition having impact strength.

11. An article manufactured from the reinforced polyamide composition described in claim 1.

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