JP6134035B2 - Polyamide molding materials, their use, and moldings made from them - Google Patents

Description

  The invention relates to a polyamide molding material according to the preamble of the independent claim 1, which molding material comprises at least one partially crystalline, partially aromatic polyamide, at least one amorphous polyamide, and a glass having a flat cross section. Contains fibers and optional additives such as flame retardants. Such molding materials are particularly suitable for the manufacture of housings or housing parts or covers or panels for electrical and electronic equipment.

  For example, housings for notebook computers or mobile phones are preferably manufactured from glass fiber reinforced plastic molding materials, generally by injection molding. They are lightweight, thin-walled and have high rigidity, low warpage and extremely good surface quality. These molding materials must be able to be processed well at the same time. That is, it must have good fluidity as a melt in injection molding, and preferably further has flame retardancy. Proposals regarding this requirement have already been made in the prior art.

  The disadvantages of all the free-flowing polyamides described in the prior art are also known as “flash” or “webbing” with glass fiber reinforced polyamide when the polyamide is subjected to a compression process and pushed into the dividing line of the mold. Is formed. As described in Friedrich Johannaber, Walter Michaeli, Handbuch Spritzgiessen [Injection Molding Handbook], 2nd edition, Hanser Fachbuchverlag 2004, ISBN 9783446229662, the degree of flash formation is optimized for mold precision and machining parameters. Can be minimized. However, since peeling of the webbing during use gives rise to dirty colors and functional interference due to the plastic particles, especially the injection-molded products described later frequently, first manually. It must be deburred in a time-consuming manner.

  In addition to manual deburring, there is a manifold automatic deburring method for injection molded products, which highlights the frequency of “flash” and emphasizes the need for post-processing.

  A polyamide molding material is disclosed in US 2010/0249292 A1, which is partially crystalline, preferably partially aromatic polyamide, amorphous, preferably partially aromatic polyamide, non-halogen flame retardant, boric acid as synergist. Contains zinc and flat glass fibers. Examples include high stiffness, low warpage, and good, glossy surface appearance. A housing for a notebook computer is cited as a preferred application.

  Although a polyamide molding material is described in WO2011 / 126794 A2 which is based on the same applicant as the applicant of the above-mentioned application and is identical in itself to having an amorphous partially aromatic polyamide and a flat glass fiber, In addition to two types of partially crystalline polyamides, that is, partially aromatic polyamides, it contains aliphatic polyamides. A further advantage is that the high surface gloss of parts made from them is maintained even in high temperature and high humidity environments. Applications relate to housings for portable electronic devices such as mobile phones, laptop computers, tablet computers and cameras.

  However, as the comparative examples of the present invention show, the polyamide molding materials described in US 2010/0249292 A1 and WO 2011/126794 A2 have noticeable burrs at a mold temperature of 90 ° C.

US2010 / 0249292A1 WO2011 / 126794 A2

Friedrich Johannaber, Walter Michaeli, Handbuch Spritzgiessen [Injection Molding Handbook], 2nd edition, Hanser Fachbuchverlag 2004, ISBN 9783446229662

  Accordingly, it is an object of the present invention to provide a polyamide molding material having high flowability, which can provide an injection molded article that exhibits high surface quality, low warpage, and / or minimal occurrence of burrs. is there.

  The polyamide molding material according to the present invention is preferred and suitable for producing housings or housing parts or covers or panel elements for electrical and electronic equipment.

This object is brought about by the present invention having a polyamide molding material with the features of claim 1. This polyamide molding material according to the invention contains:
At least one partially crystalline, partially aromatic polyamide (A);
At least one amorphous polyamide (B);
Polyamides (A) and (B) together comprise 30-60% by weight of polyamide molding material and 40-70% by weight of glass fibers (C) having a flat cross section;
0-15% by weight of at least one halogen-free flame retardant (D); and 0-10% by weight of further additives (E);
In total, components (A) to (E) constitute 100% by weight of the polyamide molding material.

FIG. 1 shows the gap dimensions of individual vents. FIG. 2 shows the end of a specimen arm having bent gap dimensions. FIG. 3 illustrates a measurement line for burr length.

  More preferably, the polyamide molding material according to the invention is 400 bar at the end of the mold arm with a melting temperature of 320 ° C. and a mold temperature of 90 ° C. and a vent gap dimension of 30 μm. In the injection molding burr formation test under the conditions of a holding pressure of 100 bar and a dynamic pressure of 100 bar, a burr having a length G of 30 μm or less is produced. Alternatively, to this requirement, the polyamide molding material according to the invention is characterized by the features of claim 3. In any case, the polyamide molding material according to the present invention is characterized in that at least one partially crystalline, partially aromatic polyamide (A) has a glass transition temperature of at least 105 ° C.

  Further preferred features and embodiments of the polyamide molding material according to the invention are derived from the dependent claims. In addition, their use and molded articles produced from them are claimed as inventions.

  In a preferred embodiment, the polyamide molding material according to the invention has at least one partially crystalline, partially aromatic polyamide (A) of 110 to 150 ° C., preferably 115 ° C. to 140 ° C., particularly preferably 115 ° C. to 135 ° C. It is characterized by having a glass transition temperature (measured using DSC) of 120 ° C., particularly preferably 120 to 135 ° C.

  The relative viscosity of the partially crystalline, partially aromatic polyamide (A) measured with 0.5 g of polyamide in 100 ml of m cresol at 20 ° C. is 1.45 to 2.0, preferably 1.5. ˜1.9, particularly preferably 1.5 to 1.8.

  The melting point of the partially crystalline, partially aromatic polyamide (A) measured using DSC is 300 to 330 ° C, preferably 305 ° C to 325 ° C, and particularly preferably 310 ° C to 325 ° C.

  If the glass transition temperature of the partially crystalline, partially aromatic polyamide (A) is too low, the polyamide molding material exhibits a significantly lower dimensional stability under heating conditions. If it is too high, this results in poor surface quality with a wavy surface and reduced fluidity.

  Overall, the glass transition temperature of the polyamide molding material is particularly preferably at least 120 ° C.

  In a further preferred embodiment, the polyamide molding material according to the invention was specifically produced at a melting temperature of 320 ° C. and a mold temperature of 90 ° C., and a dynamic pressure of 100 bar and a holding pressure of 400 bar, In the case of an injection molded, 6-arm specimen having an arm dimension of 90 × 10 × 1.5 mm, the burr length G at the end of the flow path of the mold arm having a vent gap dimension of 30 μm is preferably The maximum is 25 μm, particularly preferably 20 μm.

  In a further preferred embodiment of the polyamide molding material according to the invention, the at least one partially crystalline, partially aromatic polyamide (A) comprises PA 6T / 6I / 6, PA 6T / 10T, PA 6T / 6I, PA 6T / Selected from the group consisting of 10T / 6I / 10I and mixtures thereof.

  PA 6T / 6I / 6 preferably has a composition of 62/16/22 mol%. As a result, the glass transition temperature is 125 ° C. and the melting point is 312 ° C.

  PA 6T / 10T preferably has a composition of 18/82 mol%. As a result, the glass transition temperature is 117 ° C. and the melting point is 295 ° C.

  In 6T / 6I, the 6T component is preferably at least 60 mol%. 6T in 6T / 6I is particularly preferably 70 mol%. In PA 6T / 6I (70/30 mol%), the glass transition temperature is 130 ° C. and the melting point is 325 ° C.

In a preferred embodiment, the polyamide molding material according to the present invention comprises at least one partially crystalline, partially aromatic polyamide (A),
72.0-98.3 mol% terephthalic acid,
Consisting of 28.0 to 1.7 mol% isophthalic acid,
A 100 mol% dicarboxylic acid component;
60.0-85.0 mol% hexamethylenediamine;
Consisting of 15.0 to 40.0 mol% 1,10-decanediamine,
Synthesized from 100 mol% diamine component,
It is characterized by being PA 6T / 10T / 6I / 10I.

In a particularly preferred embodiment, the polyamide molding material according to the invention comprises at least one partially crystalline, partially aromatic polyamide (A)
75.0-95.0 mol% terephthalic acid,
100 mol% dicarboxylic acid component consisting of 25.0-5.0 mol% isophthalic acid,
60.0-75.0 mol% hexamethylenediamine;
Consisting of 25.0 to 40.0 mol% 1,10-decanediamine,
Synthesized from 100 mol% diamine component,
It is characterized by being PA 6T / 10T / 6I / 10I.

In a particularly preferred embodiment, the polyamide molding material according to the invention comprises at least one partially crystalline, partially aromatic polyamide (A)
80.0-90.0 mol% terephthalic acid,
A 100 mol% dicarboxylic acid component consisting of 20.0 to 10.0 mol% isophthalic acid;
62.0-72.0 mol% hexamethylenediamine;
Consisting of 28.0 to 38.0 mol% 1,10-decanediamine,
Synthesized from 100 mol% diamine component,
It is characterized by being PA 6T / 10T / 6I / 10I.

In a particularly preferred embodiment, the polyamide molding material according to the invention comprises at least one partially crystalline, partially aromatic polyamide (A)
86.4 mol% terephthalic acid,
A 100 mol% dicarboxylic acid component consisting of 13.6 mol% isophthalic acid;
66.7 mol% hexamethylenediamine,
Consisting of 33.3 mol% 1,10-decanediamine,
Synthesized from 100 mol% diamine component,
PA 6T / 10T / 6I / 10I.

  At least one amorphous polyamide (B) of the polyamide molding material is PA 6I / 6T, PA 6I, PA MACMI / 12, PA MACMI / MACMT / 12, PA 6I / MACMI / 12, PA 6I / 6T / MACMI / MACMT, PA 6I / 6T / MACMI / MACMT / 12, PA MACMI / MACM12, PA MXDI, PA MXDI / 6I, PA MXDI / MXDT / 6I / 6T, PA MXDI / 12I, PA 6I / 6T / 6NDA, PA MACM12, PA MACM14, PA MACM18, PA NDT / INDT, PA MACMT / 12, PA MACMI / MACMNDA, PA MACMT / MACMNDA, PA MACMI / MACM36, PA MACMT / MACM36, PA ACMT / MACM12, PA MACM6 / 11, PA 6I / 6T / MACMI / MACMT / MACM12 / 612, PA 6I / 6T / 6NDA / MACMI / MACMT / MACMNDA, laurin lactam, all or part of which can be replaced by caprolactam, and / Or preferably selected from the group consisting of MACM which can be replaced by PACM up to 20 mol% or less, preferably up to 10 mol%. With respect to the naphthalenedicarboxylic acid content (abbreviated as NDA) of the corresponding copolyamide, an amount of up to 20 mol% is preferred. The above-mentioned abbreviated polyamide nomenclature conforms to ISO1874-1: 1992 (E).

  Amorphous polyamide has a heat of fusion of up to 5 J / g, preferably up to 3 J / g, particularly preferably up to 1 J / g, in differential scanning calorimetry (DSC) according to ISO 11357 at a heating rate of 20 K / min. Is understood as a polyamide having a heat of fusion of

The relative viscosity of amorphous polyamide (B) (measured in 100 ml m-cresol at 20 ° C. using 0.5 g of polyamide) is 1.35 to 2.15, preferably 1.40 to 1. 90,
Particularly preferred is 1.45 to 1.85. The glass transition temperature (measured by DSC) of the amorphous polyamide (B) is 100 to 230 ° C., preferably 110 to 200 ° C., particularly preferably 120 to 190 ° C.

  The at least one amorphous polyamide (B) is particularly preferably PA 6I / 6T, and the ratio of isophthalic acid to the sum of isophthalic acid and terephthalic acid in PA 6I / 6T is 90 to 57 mol%, It is preferably 85 to 60 mol%, particularly preferably 75 to 60 mol%, particularly preferably 72 to 63 mol%.

  The relative viscosity of amorphous PA 6I / 6T (determined using 0.5 g of polyamide in 100 ml m-cresol at 20 ° C.) is 1.38 to 1.70, preferably 1.43 to 1. 65, particularly preferably 1.48 to 1.62. The glass transition temperature (measured by DSC) of amorphous PA 6I / 6T is 120-135 ° C.

  Regarding the quantity ratio of polyamides (A) and (B) in the polyamide molding material according to the invention, the weight ratio of at least one partially crystalline, partially aromatic polyamide (A) to at least one amorphous polyamide (B) Is in the range of 30:70 to 70:30, preferably in the range of 40:60 to 65:35, particularly preferably in the range of 40:60 to 60:40, particularly preferably 45:55 to 56:44. In the range of 45:55 to 49:51.

  At a proportion of amorphous polyamide (B) of less than 30% by weight, the polyamide molding material crystallizes too rapidly during the injection molding process, resulting in a higher crystallinity on the surface of the injection molded product. At a proportion of amorphous polyamide (B) higher than 70% by weight, the heat dimensional stability of the polyamide molding material becomes excessively low.

  The polyamide molding material according to the present invention has an HDTA (1.80 MPa) of at least 150 ° C., preferably at least 160 ° C.

  Furthermore, the polyamide molding material according to the present invention exhibits good toughness.

  The amount of polyamide (A) and (B) in the polyamide molding material according to the present invention is preferably 38 to 55% by weight, particularly preferably 43 to 55% by weight, based on 100% by weight of the polyamide molding material. .

  In a further embodiment, the polyamide molding material according to the invention contains only one polyamide (A) and one polyamide (B), respectively.

  The amount of the glass fiber (C) having a flat cross section is preferably 45 to 62% by weight, particularly preferably 45 to 57% by weight, based on 100% by weight of the polyamide molding material.

  The glass fiber used has a non-circular, flat cross section. Such glass fibers are also designated as flat glass fibers or flat glass fibers. Flat cross-sections are all shapes that are flattened in relation to a circle, ie flat cross-sections are oval, elliptical, elliptical with a constriction (so-called eyebrows), flattened, polygonal, It can be rectangular or substantially rectangular. The appearance of the glass fiber may be drawn or spiral. Short or long glass fibers can be used. The glass fibers can be made from any glass, for example, A-, C-, D-, E-, M-, S-, R-glass, or any mixture thereof can be used. Glass fibers made of E glass, glass fibers made of a mixture with E glass, or mixtures with E glass fibers are preferred.

  In the case of flat glass fiber, the aspect ratio of the cross section, that is, the ratio of the main cross section axis (longest dimension in the cross section) to the sub cross section axis (longest dimension perpendicular to the main cross section axis) is 1.5 to 8 , Preferably 2 to 6, and more preferably 3 to 5.

  The length of the cross-sectional axis of the flat glass fiber is 3 to 40 μm. Preferably, the length of the sub-section axis is 3 to 20 μm, particularly preferably 4 to 10 μm, and the length of the main section axis is 6 to 40 μm, particularly preferably 12 to 30 μm.

  Flat glass fibers can be equipped with a suitable sizing or adhesion promoter system. For this purpose, for example, systems based on silanes, titanates, polyamides, urethanes, polyhydroxy ethers, epoxides, nickel, or combinations or mixtures thereof can be used, respectively.

  The polyamide molding material according to the invention contains at least one halogen-free flame retardant (D) and is in an amount of 0 to 13% by weight, particularly preferably 9 to 13% by weight, very particularly preferably in the polyamide molding material. 10 to 12% by weight.

  Preferably, triazines, triazine derivatives, phosphaphenanthrenes, phosphazanes, phosphazenes, polyphosphazenes, metal hydroxides, phosphonic acids with synergists are used as halogen-free, ie halogen-free flame retardants.

  The at least one halogen-free flame retardant (D) preferably contains a flame retardant containing phosphorus, preferably a phosphinic acid salt. Phosphinates are understood as salts of phosphinic acid and / or diphosphinic acid and / or polymers thereof.

  Phosphinates of the general formula (I) and / or formula (II) and / or their polymers are preferably used as phosphinates:

（式中、Ｒ１、Ｒ２は、同一かまたは異なり、好ましくは線状または分岐、飽和、不飽和もしくは部分不飽和のＣ１〜Ｃ８アルキル、および／またはアリールを意味し；
Ｒ３は、線状または分岐、飽和、不飽和もしくは部分不飽和のＣ１〜Ｃ１０アルキレン、Ｃ６〜Ｃ１０のアリーレン、アルキルアリーレン、またはアリールアルキレンを意味し；
Ｍは、周期律表の第２または第３主族または副族からの金属イオンを意味し、好ましくはアルミニウム、バリウム、カルシウムおよび／または亜鉛であり；
ｍは２または３であり；
ｎは１または３であり；
ｘは１または２である。）

Wherein R 1 and R 2 are the same or different, preferably linear or branched, saturated, unsaturated or partially unsaturated C 1 -C 8 alkyl and / or aryl;
R3 represents linear or branched, saturated, unsaturated or partially unsaturated C1-C10 alkylene, C6-C10 arylene, alkylarylene, or arylalkylene;
M represents a metal ion from the second or third main group or subgroup of the periodic table, preferably aluminum, barium, calcium and / or zinc;
m is 2 or 3;
n is 1 or 3;
x is 1 or 2. )

  Preferably, aluminum, barium, calcium and zinc are used as metal ions. Suitable phosphinic acids for the production of the phosphinic acid salts according to the invention are, for example, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methane-di (methylphosphinic acid), ethane-1 , 2-di (methylphosphinic acid), hexane-1,6-di (methylphosphinic acid), benzene-1,4-di (methylphosphinic acid), methylphenylphosphinic acid, diphenylphosphinic acid. For example, phosphinic acid salts can be prepared by reacting phosphinic acid with metal carbonates, metal hydroxides, or metal oxides in aqueous solution, and the monomers are essentially reaction conditions under certain circumstances. In response to this, a polymeric phosphinate is formed.

  Nitrogen-containing compounds, nitrogen-containing and phosphorus-containing compounds, metal borates, metal carbonates, metal hydroxides, metal hydroxy oxides, metal nitrides, metal oxides, metal phosphates, metal sulfides, metal stannic acid Salts, metal hydroxystannates, silicates, zeolites, basic zinc silicates, and / or silicic acids are preferred as synergists. Aluminum, barium, calcium, magnesium, manganese, titanium, zinc, and / or tin are preferably used as the metal.

  Examples of synergists include melamine, melamine derivatives of cyanuric acid, melamine derivatives of isocyanuric acid, melamine cyanurate, melamine condensation products such as melem, melam or melon, pyrophosphoric acid and melamine condensation products or melamine Reaction products, condensation products of polyphosphoric acid and melamine or reaction products of melamine, melamine sulfate, melamine pyrosulfate, guanidine derivatives, ammonium polyphosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, aluminum hydroxide, synthetic aluminum Meta hydroxide (synthetic aluminum hydroxy oxide), natural aluminum hydroxide (natural aluminum hydroxy oxide), aluminum oxide, calcium borate, calcium carbonate, calcium carbonate, calcium oxide, Calcium oxide, iron oxide, magnesium borate, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfide, manganese hydroxide, manganese oxide, titanium nitride, titanium dioxide, zinc oxide, zinc borate, zinc carbonate, zinc hydroxide Zinc nitride, zinc oxide, zinc phosphate, zinc sulfide, zinc stannate, basic zinc silicate, tin oxyhydrate, and combinations thereof.

  In preferred embodiments, melamine cyanurate, dimelamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate, melamine pyrosulfate, dicyandiamide, ammonium polyphosphate, aluminum hydroxide, synthetic aluminum metahydroxide ( Synthetic aluminum hydroxy oxide), natural aluminum metahydroxide (natural aluminum hydroxy oxide), calcium carbonate, calcium carbonate magnesium, iron oxide, magnesium carbonate, magnesium hydroxide, zinc metaborate, zinc carbonate, zinc nitride, sulfide Zinc, zinc stannate, zinc hydroxide stannate, basic zinc silicate, and / or tin oxyhydrate are used as halogen-free flame retardants.

  Finally, the polyamide molding material according to the invention can contain up to 10% by weight of further additives (E), preferably in an amount of 0-8% by weight, particularly preferably 0.1-6% by weight, And very particularly preferably 1 to 6% by weight.

  Further additives are inorganic stabilizers, organic stabilizers, lubricants, polytetrafluoroethylene, colorants, marking substances, inorganic pigments, organic pigments, infrared absorbers, antistatic agents, antiblocking agents, conductive additives Agent, carbon black, graphite, carbon nanotube, mold release agent, release agent, brightening agent, photochromic additive, other polymer impact toughness improver, adhesion promoter, anti-drip agent, metal pigment, metal glitter, metal coating Can be selected from the group consisting of particles, fillers and reinforcing agents, in particular nanoscale fillers and reinforcing agents, for example minerals having a particle size of approximately 100 nm, or unmodified or modified, natural or synthetic phyllosilicates or mixtures thereof .

  Additional additives can be added in masterbatch form. Polyamide is preferably used as the base polymer of the masterbatch. The poly-amide is preferably selected from the group consisting of PA6, PA66, PA12, PA1012 PA1212 PA6 / 12, PA6 / 66, PA6 / 69, and mixtures thereof. By using the master batch, the amount of polyamide introduced into the polyamide molding material according to the present invention is 5% by weight or less, preferably 3% by weight or less in relation to the total of the polyamide molding material.

  Lubricants include ethylene bis stearamide, oleic amide, stearic amide, aluminum tristearate, oxidized or non-oxidized polyethylene wax, oxidized or non-oxidized polypropylene wax, salt of oxidized or non-oxidized polyethylene wax, oxidized or non-oxidized type Selected from the group consisting of polypropylene wax salts, monocarboxylic acids, dicarboxylic acids, monocarboxylic acid salts, dicarboxylic acid salts, monocarboxylic acid esters, dicarboxylic acid esters, and mixtures thereof. The lubricant is preferably added in an amount of 2% by weight or less in relation to the total polyamide molding material.

  Among monocarboxylic acids, stearic acid, palmitic acid, arachidic acid, behenic acid, montanic acid, lauric acid, myristic acid, 12-hydroxystearic acid and mixtures thereof are preferred. Of the dicarboxylic acids, naphthalenedicarboxylic acid, isophthalic acid, terephthalic acid, and mixtures thereof are preferred.

  For the salt, barium, calcium, magnesium, zinc, potassium, copper and / or cobalt salts are preferably used.

  In the polyamide composition according to the present invention, for example, an antioxidant, an ozone degradation inhibitor, a photoprotective agent, a UV stabilizer, a UV absorber, or a UV blocker can be used as a stabilizer or an aging protectant, respectively.

  All particulate fillers known to those skilled in the art can be considered as fillers. These include, in particular, minerals, talc, mica, dolomite, silicate, quartz, titanium dioxide, wollastonite, kaolin, silicic acid, magnesium carbonate, magnesium hydroxide, chalk, crushed glass, glass flakes, crushed carbon fiber, crushed Or precipitated calcium carbonate, limestone, feldspar, barium sulfate, magnetic or magnetizable metals or alloys, glass beads, hollow glass beads, hollow sphere silicate fillers, synthetic layered silicates, natural layered silicates, and mixtures thereof A particulate filler selected from is included.

  The further reinforcing agent is selected from fibrous or reinforcing fillers known from those skilled in the art, preferably selected from the group consisting of carbon fibers, metal fibers, aramid fibers, polymer fibers, whiskers, mineral fibers, and mixtures thereof. The

  A whisker should be understood as an acicular single crystal made of metal, oxide, boride, carbide, nitride, polytitanate, carbon, etc., and typically has a polygonal cross section, for example Potassium titanate, aluminum oxide, silicon carbide whiskers and mixtures thereof. Whiskers typically have a diameter of 0.1-10 μm and a length in the millimeter to centimeter range. They have a high tensile strength at the same time. Whiskers can be manufactured from vapor phase deposition (VS mechanism) or three-phase deposition (VLS mechanism)

  A filler or reinforcing agent may be surface treated. This can be done using a suitable sizing or adhesion promoter system. For this purpose, for example, systems based on fatty acids, waxes, silanes, titanates, polyamides, urethanes, polyhydroxy ethers, epoxides, nickel, or combinations or mixtures thereof can be used, respectively. .

  In the polyamide composition of the present invention, for example, kaolin, serpentine, talc, mica, vermiculite, muscovite, illite, smectite, saponite, montmorillonite, hectorite, double hydroxide, or a mixture thereof as a layered silicate Can be used. The layered silicate may be surface (modified) or untreated (unmodified).

  In the polyamide composition according to the present invention, for example, carbon black and / or carbon nanotubes are also referred to as carbon nanofibrils, and can be used as an antistatic agent and / or a conductive additive. The use of carbon black, however, can be used to improve the black coloration of the polyamide composition.

  The polyamide molding material according to the present invention is injection molded at a mold temperature of 90 ° C. and a melting temperature of 320 ° C., and in a standard test specimen having a plate-like dimension of 60 × 60 × 2 mm, according to ISO standard 294 The warpage calculated as the difference in the work shrinkage in the longitudinal direction is advantageously characterized by 0.22% or less, preferably 0.19% or less.

  The relative rating scale used for visibility of seams, sink marks and surface quality is based on end customer quality requirements for injection molded cell phones and laptop housings. Grade 1 shows the entire surface of the corresponding injection-molded part in the raw state and after the possible metal plating completely uniformly at any viewing angle, without the spread of seams or ribs located under the surface Means that. Grade 2 for surface quality means that slight glass fiber erosion is perceived at locations away from the sprue when an intentionally delayed injection rate is used. With respect to sink marks and seams, Grade 2 is recognized as an untreated condition where significant problems are observed in oblique incident light. In grade 2, all kinds of irregularities can be clearly recognized, which prevents subsequent metal plating on the surface portion. Grade 3 or lower is no longer accepted by the end customer. In order to produce a polyamide molding material, the polymer components are melted and mixed in a viscous molten state. Reinforcing material (glass fibers) can be metered into the inlet via a gravimetric scale with the polymer component or metered into the melt via side flow. This is done, for example, using a typical compounding machine, a single or twin screw extruder or a screw kneader. Other components (additives, color pigments) can be fed into the inlet with the polymer component, in particular separately via a side stream or in the form of a dry mixture.

  The dry granules and any further additives are mixed for the dry mix product. The mixture is homogenized for 10 to 40 minutes using a tumble mixer, drum hoop mixer, rotary dryer. In order to avoid moisture absorption, this may be done under dry protective gas.

  Compounding takes place at a series of cylinder temperatures from 250 ° C to 320 ° C. A vacuum may be applied to the atmospheric pressure before the nozzle, or deaeration may be performed. The melt is extruded into strands, cooled in a water bath at 10-80 ° C. and subsequently granulated. The granules are dried under nitrogen atmosphere or vacuum conditions at 80-120 ° C. for 12-24 hours to a moisture content of less than 0.1% by weight.

  Molded articles produced by injection molding from the polyamide molding material according to the invention, in particular, the molded article has an amorphous or less crystallized surface area and a partially crystalline core area. It is characterized by that.

  The polyamide molding material of the present invention is preferably an electric / electronic device, OA device, hi-fi and TV device, entertainment device, stationary or portable computer, in particular laptop computer, notebook computer, netbook, tablet PC, game. Machine, lighting device, preferably lighting device having LED, equipment incorporated in automobile dashboard, navigation equipment, measuring equipment, personal digital assistant, communication equipment, camera, clock or table clock, computer, electronic storage device, keyboard, music Preferably used for recorders, digital music playback devices (eg CD, MP3 (registered trademark) player, iPod (registered trademark)), e-books, mobile phones, and smartphone housings or housing parts or cover and panel element injection moldings The That.

  The invention will now be described in greater detail on the basis of the following examples which merely illustrate the invention but do not limit it.

  The following materials were used in the examples and comparative examples as shown in Table 1a (polyamide) and Table 1b (additives).

Preparation of polyamide molding materials for examples and comparative examples Dry polyamide granules were mixed with additives. This mixture was homogenized for 30 minutes under protective gas using a tumble mixer. This dry blend was metered into the inlet of a Werner & Pfleiderer type ZSK25 twin screw extruder using a scale.
The glass fibers were conveyed into the melt through the side stream of an extruder equipped with 6 housing units before the nozzle. The temperature of the first housing was set to 80 ° C and the remaining housing temperature was set to 310 ° C. Atmospheric deaeration was performed using a speed of 200 RPM and an extrusion rate of 15 kg / h. The strands were cooled in a water bath and cut, and the resulting granules were dried at 120 ° C. under vacuum conditions (residual pressure 50 mbar) for 24 hours so that the water content was less than 0.1% by weight.

  Unless otherwise stated, test specimens were then made from the granules on an Arburg type Allrounder 420 C 1000-250 injection molding machine. A polyamide molding material melt temperature of 320 ° C. and a mold temperature of 90 ° C. were set. The specimen was stored on silica gel for 48 hours at room temperature before measurement.

Measurements were performed according to the following test methods and standards.
Spiral Flow Test A flow spiral was produced using an Arburg model Allrounder 320-210-750 injection molding machine at a melting temperature of 320 ° C. and a mold temperature of 90 ° C. with an injection pressure of 1000 bar. The flow spiral had their sprue gate in the center and had a cross section of 1.5 × 10 mm. The following distance markers were applied to the spiral:
・ Points with 1mm intervals ・ Strokes, all centimeters ・ Length specification 5 centimeters each

Tensile modulus:
ISO 527, tensile speed 1 mm / min ISO tension bar, standard: ISO / CD 3167, type A1, 170 × 20/10 × 4 mm, temperature 23 ° C

Relative viscosity (RV)
ISO307
0.5 g polyamide in 100 ml m-cresol Temperature 20 ° C
Relative viscosity (RV) is calculated according to RV = t / t _o based on the reference section 11

Melting point (Tm) and glass transition temperature (Tg)
Standard 11357
Granules with a moisture content of less than 0.1% by weight

  Differential scanning calorimetry (DSC) was performed at a heating rate of 20 K / min. For the melting point, the temperature was specified at the peak maximum. The glass transition temperature was specified at the starting point.

HDT (heat distortion temperature, heat dimensional stability)
ISO75
ISO test bar, standard: ISO / CD 3167, type B1, 80 × 10 × 4 mm
HDT A Load 1.08MPa

Burr formation test:
The mold used to determine the occurrence of burrs is a two-plate mold with a 6-arm specimen with a central sprue gate. The length, width, and thickness of the arm are 90 × 10 × 1.5 millimeters. Vents are placed at the start and end of each arm. The vents at the end of the flow path have different gap dimensions. As shown in FIG. 1, the gap dimensions of the individual vents are 0, 4, 8, 12, 20 and 30 μm. The bend width is 2.95 millimeters (see FIG. 2). The burr length G (see FIG. 3) of the test body was evaluated at the end of the arm having a vent gap size of 30 μm. In the details of FIGS. 2 and 3 showing the end of a specimen arm having a 30 μm bent gap dimension, the components are not drawn to scale, but are shown schematically and the principle can be understood therefrom. In FIG. 3, the material burr that penetrates into the vent gap at the end of the flow path and protrudes beyond the end of the specimen arm is exaggerated and the burr length G is defined.

  These specimens were produced using an injection molding machine of the form Krauss Maffei 100-380CX. Since there was a risk of burrs being damaged, parts were removed by hand. The injection speed is 100 mm / s, the screw speed is 50 RPM, the dynamic pressure is 100 bar, and the holding pressure is 400 bar. 320 ° C. was used as the melting temperature and 90 ° C. was used as the mold temperature.

  The burr length G is measured on the basis of an image recorded using a model Leica / Wild M420 micrograph at a magnification of 40-50 times by using a 2.0X focus lens, and the burr is at its full width. Was filmed. The burr length G is caused by the distance between the base line (the end of the specimen) and the measurement line. A measurement line is laid so that the areas of the dents and bulges are complemented (see FIG. 3). An arithmetic average value is defined from the measured values of five different specimens.

Processing shrinkage:
ISO294-4
Plate, mold D2, 60 × 60 × 2 mm (according to standard ISO 294-3).
The plate is formed at a melting temperature of 320 ° C. and a mold temperature of 90 ° C. These are stored on silica gel for 48 hours at room temperature before measurement. Work shrinkage is measured in the longitudinal and transverse directions with respect to the flow direction in relation to the dimensions of the mold cavity. The arithmetic average value is calculated from the measured values for the five plates.

Combustion test
Use UL-94 of Underwriters Laboratories Test bar 125 × 13 × 0.45mm
Each of the five specimens is conditioned at 23 ° C for at least 48 hours and 50% relative humidity (UL-94 point 6.1). Each of the five specimens is conditioned at 70 ° C. for 168 hours and then cooled in a dryer for at least 4 hours at room temperature (UL-94 point 6.1). Two sets of 5 specimens are each subjected to a vertical burn test, in which each combination must withstand. In the vertical burn test, five sets of specimens are exposed to the flame twice for each. Class V0 is provided when the self-extinguishing properties of the individual specimens occur within 10 seconds, with the total combustion length of both flame exposures in all 5 specimens being up to 50 seconds. Self-extinguishing and smoldering after the second flame exposure should be terminated after 30 seconds on each specimen. The specimen cannot be burned out until the chucking clamp. Probably the resulting drip will not ignite the cotton wool.

  Four examples 1 to 4 according to the present invention are shown in Table 2 below. Example 4 is a modification of the flame retardant.

  In these four examples according to the present invention, the polyamide molding material according to the present invention is very surprised that the appearance is good to extremely good (even if it is a modified example of the flame retardant) and the extremely low warpage is shown. Clarify that it has a positive effect.

  This effect according to the present invention is a test that can be directly compared with the embodiment according to the present invention, because it is prepared, blended, injection molded and tested in the same method and apparatus according to the conventionally known polyamide molding materials. It is very clearly shown by direct comparison of the bodies. The one obtained from the procedure described in the prior art was reproduced. Comparative Examples 5 to 11 are shown in Table 3 below.

  The molding material of Comparative Example 5 having circular glass fibers exhibits poor surface quality and significant warpage. Comparative Example 6, which has flat glass fibers and shows a low glass transition temperature, has good surface quality, but has strong sink marks. The molding material of Comparative Example 6 also has a very strong burr formation.

  The molding materials of Comparative Examples 9 and 10 corresponding to US 2010/0249292 A1 and the molding material of Comparative Example 11 corresponding to WO2011 / 126794 A2 display the occurrence of strong burrs. Finally, the molding materials of comparative examples 7 and 8 corresponding to EP2354176 A1 show poor evaluation in all respects.

  EP2354176 A1 is a partially crystalline, partially aromatic polyamide (A) as a polyamide component in molding materials that can produce parts that can be soldered at temperatures higher than 260 ° C. without forming bubbles during the soldering process. Disclosure.

  Considering the latter situation, it is more surprising and completely unexpected to use the polyamide according to EP2354176 A1, but the new polyamide molding material according to the present invention has the advantages of burr formation, warpage and surface It is significantly better in terms of the significant effects achieved with respect to quality than those provided with EP2354176 A1 and the closest prior art.

  Thus, the polyamide molding material according to the present invention may have an improved combination of properties with respect to burr formation, warpage, sink marks and / or surface quality as compared to known related prior art polyamide molding materials. This is shown in the examples.

Claims (23)

PA 6T / 6I / 6 and / or PA 6T / 10T, and is selected from the group consisting of a mixture comprising a PA 6T / 10T / 6I / 10 I, part partial crystallinity, partially aromatic polyamide (A);
At least one amorphous polyamide (B),
Partial crystallinity, the weight ratio of the partially aromatic polyamide (A) Tai該least one amorphous polyamide (B) is 30: 70-70: Yes 30 range;
The polyamides (A) and (B) together constitute 30-60% by weight of the polyamide molding material; and
40-70% by weight of glass fiber (C) having a flat cross section;
0-15% by weight of at least one halogen-free flame retardant (D); and 0-10% by weight of a further additive (E),
Inorganic stabilizers, organic stabilizers, lubricants, polytetrafluoroethylene, colorants, marking substances, inorganic pigments, organic pigments, infrared absorbers, antistatic agents, antiblocking agents, conductive additives, carbon black, graphite , Carbon nanotubes, mold release agents, release agents, optical brighteners, photochromic additives, adhesion promoters, anti-dripping agents, metal pigments, metal glitter, metal coated particles, fillers and reinforcing agents, or mixtures thereof The additive (E) selected from the group;
A polyamide molding material comprising:
Components (A) to (E) together make up 100% by weight of the polyamide molding material, the polyamide molding material comprising a melting temperature of 320 ° C. and a mold temperature of 90 ° C., and a vent gap of 30 μm holding pressure of 400bar at a flow path end of the mold arms having dimensions, in the injection molding burr formation test by the dynamic pressure of 100 bar, resulting burr having a length of less than G 30 [mu] m, and unit partial crystallinity, partially The polyamide molding material characterized in that the aromatic polyamide (A) has a glass transition temperature of at least 105 ° C. The polyamide PA 6T / 10T / 6I / 10I is
72.0-98.3 mol% terephthalic acid and
Consisting of 28.0 to 1.7 mol% isophthalic acid,
A 100 mol% dicarboxylic acid component;
60.0-85.0 mol% hexamethylenediamine and
Consisting of 15.0 to 40.0 mol% 1,10-decanediamine,
The polyamide molding material according to claim 1, which is a polyamide synthesized from a 100 mol% diamine component. The polyamide PA 6T / 10T / 6I / 10I is
75.0-95.0 mol% terephthalic acid and
Consisting of 25.0-5.0 mol% isophthalic acid,
A 100 mol% dicarboxylic acid component;
60.0-75.0 mol% hexamethylenediamine and
Consisting of 25.0 to 40.0 mol% 1,10-decanediamine,
The polyamide molding material according to claim 1, which is a polyamide synthesized from a 100 mol% diamine component. The polyamide PA 6T / 10T / 6I / 10I is
80.0-90.0 mol% terephthalic acid and
100 mol% dicarboxylic acid consisting of 20.0 to 10.0 mol% isophthalic acid;
62.0-72.0 mol% hexamethylenediamine and
Consisting of 28.0 to 38.0 mol% 1,10-decanediamine,
The polyamide molding material according to claim 1, which is a polyamide synthesized from a 100 mol% diamine component. Parts partial crystallinity, relative viscosity of partially aromatic polyamide (A), 20 ° C., when measured using 0.5g polyamide in 100 ml m-cresol, characterized in that it is a 1.45 to 2.0 The polyamide molding material according to any one of claims 1 to 4. The at least one amorphous polyamide (B) is PA 6I / 6T, PA 6I, PA MACMI / 12, PA MACMI / MACMT / 12, PA 6I / MACMI / 12, PA 6I / 6T / MACMI / MACMT, PA 6I. / 6T / MACMI / MACMT / 12, PA MACMI / MACM12, PA MXDI, PA MXDI / 6I, PA MXDI / MXDT / 6I / 6T, PA MXDI / 12I, PA 6I / 6T / 6NDA, PA MACM12, PA MACM14, PA MACM18, PA NDT / INDT, PA MACMT / 12, PA MACMI / MACMNDA, PA MACMT / MACMNDA, PA MACMI / MACM36, PA MACMT / MACM36, PA MACMT / MACM12, PA MACM / 11 is selected from the group consisting of PA 6I / 6T / MACMI / MACMT / MACM12 / 612, PA 6I / 6T / 6NDA / MACMI / MACMT / MACMNDA,
6. Laurin lactam can be replaced in whole or in part by caprolactam, and / or MACM can be replaced by PACM in a proportion of up to 20 mol% or less. Polyamide molding material.   The at least one amorphous polyamide (B) is PA 6I / 6T, and the ratio of isophthalic acid to the total of isophthalic acid and terephthalic acid in PA 6I / 6T is 90 to 57 mol%. The polyamide molding material according to claim 6. Parts partial crystallinity, the weight ratio of the partially aromatic polyamide (A) to the at least one amorphous polyamide (B) is 40: 60-65: characterized in that it is a range of 35, claims 1 to 7 The polyamide molding material of any one of these. At least one halogen-free flame retardant (D) is present in the polyamide molding material, characterized in that it is added in an amount of 0-13% by weight, the polyamide according to any one of claims 1-8 Molding material. The polyamide molding material according to claim 9 , wherein the at least one halogen-free flame retardant contains a flame retardant containing phosphorus. Injection molded at 90 ° C. of mold temperature and 320 ° C. of the melting temperature, has a plate-like dimensions of 60 × 60 × 2 mm, standard test body produced from the molding material, according to ISO standard 294, transverse characterized in that it has in the longitudinal direction of the processing value of 0.22% or less warpage calculated as the difference between shrinkage and polyamide molding material according to any one of claims 1-10. In particular, electrical / electronic equipment, OA equipment, hi-fi and TV equipment, entertainment equipment, stationary or portable computers, in particular laptop computers, notebook computers, netbooks, tablet PCs, game machines, lighting devices, preferably LEDs Lighting device, equipment incorporated in automobile dashboard, navigation device, measuring device, personal digital assistant, communication device, camera, clock, computer, electronic storage device, keyboard, music recorder, digital music player, electronic book, Use of the polyamide molding material according to any one of claims 1 to 10 for injection molding housings or housing parts or covers and panel elements for mobile phones and smartphones. Parts partial crystallinity, relative viscosity of partially aromatic polyamide (A), 20 ° C., when measured using 0.5g polyamide in 100 ml m-cresol, characterized in that it is a 1.5 to 1.9 The polyamide molding material according to any one of claims 1 to 4. The at least one amorphous polyamide (B) is PA 6I / 6T, PA 6I, PA MACMI / 12, PA MACMI / MACMT / 12, PA 6I / MACMI / 12, PA 6I / 6T / MACMI / MACMT, PA 6I. / 6T / MACMI / MACMT / 12, PA MACMI / MACM12, PA MXDI, PA MXDI / 6I, PA MXDI / MXDT / 6I / 6T, PA MXDI / 12I, PA 6I / 6T / 6NDA, PA MACM12, PA MACM14, PA MACM18, PA NDT / INDT, PA MACMT / 12, PA MACMI / MACMNDA, PA MACMT / MACMNDA, PA MACMI / MACM36, PA MACMT / MACM36, PA MACMT / MACM12, PA MACM / 11 is selected from the group consisting of PA 6I / 6T / MACMI / MACMT / MACM12 / 612, PA 6I / 6T / 6NDA / MACMI / MACMT / MACMNDA,
6. Laurin lactam can be replaced in whole or in part by caprolactam and / or MACM can be replaced by PACM in a proportion of up to 10 mol% or less. Polyamide molding material.   The at least one amorphous polyamide (B) is PA 6I / 6T, and the ratio of isophthalic acid to the total of isophthalic acid and terephthalic acid in PA 6I / 6T is 85 to 60 mol%. The polyamide molding material according to claim 6.   The at least one amorphous polyamide (B) is PA 6I / 6T, and the ratio of isophthalic acid to the total of isophthalic acid and terephthalic acid in PA 6I / 6T is 75 to 60 mol%. The polyamide molding material according to claim 6.   The at least one amorphous polyamide (B) is PA 6I / 6T, and the ratio of isophthalic acid to the total of isophthalic acid and terephthalic acid in PA 6I / 6T is 72 to 63 mol%. The polyamide molding material according to claim 6. Parts partial crystallinity, the weight ratio of the partially aromatic polyamide (A) to the at least one amorphous polyamide (B) is 40: 60 to 60: characterized in that it is a range of 40, claims 1 to 7 The polyamide molding material of any one of these. Parts partial crystallinity, the weight ratio of the partially aromatic polyamide (A) to the at least one amorphous polyamide (B) is 45: 55-56: wherein the 44 is in the range of, claims 1 to 7 The polyamide molding material of any one of these. Parts partial crystallinity, the weight ratio of the partially aromatic polyamide (A) to the at least one amorphous polyamide (B) is 45: 55 to 49: and wherein the 51 is in the range of, claim 1 8. The polyamide molding material according to any one of 7 above. The polyamide according to any one of claims 1 to 8 , characterized in that at least one halogen-free flame retardant (D) is added to the polyamide molding material in an amount of 9 to 13% by weight. Molding material. The polyamide according to any one of claims 1 to 8 , characterized in that at least one halogen-free flame retardant (D) is added to the polyamide molding material in an amount of 10 to 12% by weight. Molding material. The polyamide molding material according to claim 9 , characterized in that the at least one halogen-free flame retardant comprises a flame retardant comprising phosphinic acid and / or diphosphinic acid and / or salts of their polymers.

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