JPH0241548B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention focuses on the scratch resistance and physical property balance (particularly rigidity, heat resistance, The present invention relates to a colored resin composition having good properties (hardness and impact resistance). By blending fillers with thermoplastic resin, we can improve the rigidity, heat resistance, combustibility, dimensional stability, flame retardance,
It is well known to improve printability, paintability, adhesion, impact resistance, etc. These methods are effective in improving each property, but conversely, when linear scratches occur on the surface of the molded product due to abrasion of foreign substances, the scratches turn white and lose commercial value, i.e., the scratch resistance It has the disadvantage that it worsens. As a method to improve this drawback, for example, a method of adding a specific metal compound (Japanese Unexamined Patent Publication No. 54-33553,
54-43250), a method of adding a specific resin component (JP 56-41237), a method of using a specific filler together (JP 55-45715, JP 55-120642, JP 57)
-16042, No. 57-8235, No. 57-73033), methods using specific rubber components, etc. (Japanese Patent Application Laid-open No. 57-73034), methods using specific polypropylene (Japanese Patent Application Laid-Open No. 56-88447), etc. Many proposals have been made. Each of these methods has been found to be effective to some extent, and has made it possible to apply propylene resins to various fields where appearance is important, including the field of industrial parts. However, these methods have not been able to satisfy the extremely high requirements for scratch resistance of molded bodies in recent years, and further improvement methods are desired. The present invention aims to improve these unsatisfactory points of the prior art, and uses a specific pigment, a filler, a specific amount of an ethylene polymer, and optionally a rubber, to produce a specific crystalline propylene-ethylene copolymer. This was done based on the discovery that the scratch resistance of the resin is greatly improved when the compound is blended with the resin. That is, the present invention consists of the following components (a) to (e), and the ratio of (a), (b), (c), and (d) is (a) + (b) + (c) + (
d)
30-90% by weight, 20-5% by weight, respectively.
40 to 0% by weight and 35 to 5% by weight, and the blending ratio of (e) to (a) + (b) + (c) + (d) is 1 to 10% by weight. A filler-containing colored propylene polymer composition. (a) Propylene with an ethylene content of 2 to 15% by weight, a boiling xylene soluble content of 4 to 15% by weight, and an average dispersion diameter of domains consisting of a polyethylene portion and an amorphous propylene-ethylene copolymer portion of 2.0μ or less - Ethylene block or random copolymer (b) Ethylene polymer with a density of 0.920 g/cm ³ or more and a melt flow rate of 0.1 to 50 g/10 min (c) Propylene content of 20 to 60% by weight, Mooney density
ML ₁₊₄ (100℃) 15-120 ethylene-propylene copolymer rubber (d) Talc with average particle size 0.2-5μ and talc 0.1-0.5μ
At least one filler selected from barium sulfate (e) with an average particle size of 0.2 μ or less and a specific surface area of 25 m ² /
A pigment consisting of a coloring component ○A and a dispersant ○B in which the component of 1g or more accounts for at least 30% by volume, and the blending ratio of ○A and ○B [○B/○B] is 0.4 to 9 by weight (however, The average dispersion diameter of the domains and the average particle diameter of the pigment were measured using an electron microscope, the average particle diameter of the filler was measured using a light transmission method using a liquid phase sedimentation method, and the specific surface area was measured using a gas adsorption method. The composition of the present invention not only has significantly improved scratch resistance, but also has a good balance of physical properties, especially stiffness, heat resistance, and impact resistance, so it is suitable for fields that require a high level of quality. can be applied. The crystalline propylene polymer, which is the component (a) used in the present invention, has an ethylene content of 2 to 15% by weight, a boiling xylene soluble content of 4 to 15% by weight, and a polyethylene portion and an amorphous propylene-ethylene copolymer. The polymer is a propylene-ethylene block or random copolymer in which the average dispersion diameter of the domains consisting of two parts is 2.0μ or less, preferably 1.5μ or less. Here, the measured value of ethylene content is obtained by a conventional method using infrared spectrum analysis and NMR, and the boiling xylene soluble content is measured by immersing 2 g of the sample in 300 c.c. of boiling xylene for 30 minutes. The value is determined by back calculation from the weight of the solid phase obtained by dissolving it in water, cooling it to room temperature, filtering it with a G4 type glass filter, and drying it. The average dispersion diameter of the domains is measured by subjecting the fractured surface of a molded test piece to an appropriate etching treatment to make the domain portion stand out, and then observing it with an electron microscope to determine the value. As a specific calculation method, for example, there is a method using an image analyzer. If the ethylene content of this component is less than 2% by weight, it is unfavorable in terms of impact strength, while if it exceeds 15% by weight, the rigidity is insufficient. In addition, those with a boiling xylene soluble content of less than 4% by weight are unfavorable in terms of impact strength, while 15% by weight
Anything in excess has insufficient scratch resistance and rigidity. Furthermore, a domain having an average dispersed diameter of more than 2.0 μm is unfavorable in terms of scratch resistance, impact strength, and rigidity. Such a propylene-ethylene polymer must be crystalline, and its isotactic index (II) is generally 40 or more, preferably 60 or more. Those with an II of less than 40 are unsuitable due to lack of scratch resistance, rigidity, hardness, etc. In addition, the MFR of this component (JIS-K7210, 230℃,
2.16Kg load) is 0.01 to 200g/10 minutes, especially
Preferably, the amount is 0.1 to 100 g/10 minutes. If the MFR is less than 0.1 g/10 minutes, the moldability and appearance are not good, and if it exceeds 200 g/10 minutes, the impact resistance is poor and unsuitable. Next, the ethylene polymer which is the component (b) used in the present invention has a density of 0.920 g/cm ³ or more, preferably 0.930 g/cm ³ or more, and the types include:
Homopolymers of ethylene (polyethylene), ethylene and other α-olefins (e.g. propylene, butene, pentene, hexene, heptene, etc.) or unsaturated organic acids and their anhydrides (e.g. acrylic acid, methacrylic acid, maleic acid, anhydride, etc.) (maleic acid, itaconic acid, etc.) or unsaturated esters (e.g. vinyl acetate, methyl acrylate, methyl methacrylate, etc.), vinyl monomers such as vinyl silane or aromatic vinyl compounds, etc., or two or more block, random or graft copolymers. Examples include merging. Furthermore, a mixture of these polymers may also be used. In the case of the above copolymer of ethylene and other vinyl monomers, ethylene must account for at least a majority by weight. MFR of these ethylene polymers (JIS-K7210,
190°C, 2.16Kg load) is 0.1 to 50g/10 minutes. Also, among these ethylene polymers, the density is
If it is less than 0.920 g/cm ³ , the effect of improving scratch resistance is low, and it is not preferable in terms of rigidity and weld strength. Among these ethylene polymers, polyethylene is particularly preferred. Such ethylene polymers further improve scratch resistance, but are also effective in improving impact resistance. In addition, the ethylene-propylene copolymer rubber used in the present invention, which is the component (c) above, is a binary copolymer (EPM) consisting of ethylene and propylene or a ternary copolymer consisting of ethylene, propylene, and a non-conjugated diene. (EPDM) with a propylene content of 20-60% by weight, preferably 25-50%
Weight% and Mooney viscosity ML ₁₊₄ (100℃) from 15 to
120, preferably between 20 and 100.
For EPDM, those with an iodine value of 20 or less are good. Propylene contents outside the above range are not preferred in terms of impact strength, those with a Mooney viscosity of less than 15 have poor scratch resistance, and those with a Mooney viscosity of more than 120 have poor moldability and appearance. Next, the filler which is the component (d) used in the present invention is talc with a surface-treated or untreated average particle diameter of 0.2 to 10μ, preferably 0.2 to 5μ, and barium sulfate with a surface treatment of 0.1 to 0.5μ. At least one selected from the following is suitable. Among them, talc is measured using a constant pressure ventilation method based on the air permeation method (for example, Shimadzu SS).
-100 type) with a specific surface area of 30,000 cm ² /g or more, and a particle size distribution of 10 μ by liquid phase sedimentation light transmission method.
Talc is preferably 95% by weight or more below, 85% by weight or above below 5μ, and 5 to 95% by weight below 1μ. If the filler is outside the above-mentioned size range, the effects of the present invention will not be sufficiently exhibited. Examples of surface treatments include silane coupling agents, higher fatty acids, fatty acid metal salts, unsaturated organic acids or their derivatives (maleic anhydride,
(acrylic acid type, etc.), organic titanate type, resin acid type,
Mention may be made of chemical or physical surface treatments with various treatment agents such as polyethylene glycol ether. In addition to the effects of the present invention, surface treatment improves mechanical strength,
It is effective in improving printability, weld strength, paintability, adhesiveness, tapping property, moldability, kneading property, etc. Here, the average particle diameter of the filler is a value measured by a light transmission method using a liquid phase sedimentation method. Furthermore, the pigment used in the present invention, which is the above component (e), has an average particle size of 0.2μ or less, preferably 0.18μ or less, and a specific surface area of 25m ² /g or more, which accounts for at least 30% by volume of the coloring component. It consists of A and a dispersant ○B, and the blending ratio of ○A and ○B [○B/○B] is the weight ratio.
0.4 to 9. However, the average particle diameter means a value measured by an electron microscope, and the specific surface area means a value measured by a gas adsorption method. Specifically, the average particle size is determined by measuring the colored component particles within an arbitrary measurement field using an electron microscope and finding the average value, and the specific surface area is determined by plotting the amount of adsorbed gas against its equilibrium pressure. From the isothermal adsorption curve,
Determine the amount of gas required for the surface of the particle to be covered with a monomolecular film of adsorbed gas molecules (therefore, the number of gas molecules), and calculate the surface area of the particle from that value and the average cross-sectional area per adsorbed gas molecule. How to (e.g.
BET method). The component A may be either inorganic or organic, or a mixture thereof, and may also be a natural product or a synthetic product. The manufacturing method is also not limited. The specific coloring component that needs to occupy at least 30% by volume of the coloring component A is a coloring component with an average particle size of 0.2 μ or less and a specific surface area of 25 m ² /g or more,
Specific examples include: Blue: Phthalocyanine Blue, Phthalocyanine Green Yellow: Quinophthalone Yellow, Isoindolinone Yellow, Polyazo Yellow, Hansa Yellow Red: Alizarin Lake, Quinacridone Red, Perylene Red, Polyazole Black: Carbon Black, Aniline Black Other coloring components include, for example, blue color: ultramarine, navy blue yellow color: yellow yellow lead, medium yellow lead red color: red iron oxide, iron oxide black color: iron black, and the like. These coloring components can be used regardless of the presence or absence of the above-mentioned surface treatment, and can also be used in combination. ○A component with an average particle size of 0.2 μ or less and a specific surface area of 25
The effect of the present invention is obtained when the coloring component with a size of m ² /g or more is less than 30% by volume, that is, when the coloring component with an average particle size of more than 0.2μ or a specific surface area of less than 25m ² /g is 30% or more by volume. I can't demonstrate my abilities. This component (e) essentially consists of a blend of the above-mentioned component (○) and a dispersant, which is the component (○) and (b) described next, in a specific ratio. As the dispersant, ordinary metal soaps and surfactants can be used, such as calcium of higher fatty acids such as stearic acid and lauric acid,
These include metal salts such as magnesium, aluminum, and zinc; polyalkylene glycols such as polyethylene glycol and polypropylene glycol, or salts thereof; polyethylene powder, and the like; these may also be used in combination. The mixing ratio of the above-mentioned coloring component (A) and the dispersant (B) is preferably such that the weight ratio [A/B] is 0.4 to 9.
When this value exceeds 9, the dispersion of the coloring component is poor, and when it is less than 0.4, the scratch resistance of the resin molded article becomes unsatisfactory, and the mechanical strength also decreases due to the dispersibility. The particle size and specific surface area of the coloring component dispersed in the resin composition containing component (e) can be measured by separating the components of the composition using an organic solvent extraction method (e.g. xylene extraction method). During ~
After dipping and dissolving it at 140 to 150°C for about 1 to 2 hours and separating the coloring component and filler from the resin using cylindrical paper, or baking the composition to take out the filler and coloring component, There is a method of separating the filler (for example, by dissolving the filler with an acid or the like) and obtaining a measured value for the extracted coloring component. In addition to the above-mentioned components ○A and ○B, other components such as fillers and modifiers can also be blended into such component (d). The blending ratio of components (a) to (e) as described above is (a),
Components (b), (c) and (d) are each 30 to 90% by weight, preferably 40 to 85% by weight, based on the total amount of (a) + (b) + (c) + (d).
(b) 20 to 5% by weight, preferably 10 to 5% by weight, (c) 40 to 0% by weight, (d) 35 to 5% by weight, and (e) component is (a) + (b). ) + (c) + (d) 1 per 100 parts by weight of the total amount
~10 parts by weight, preferably 1 to 6 parts by weight. The preferred blending ratio of component (c) varies depending on the use of the composition of the present invention, and is 20 to 5% by weight, particularly 15 to 5% by weight for applications requiring relatively high rigidity.
40 to 10% by weight, especially 40 to 20% by weight for applications requiring relatively high impact resistance, especially low-temperature impact resistance.
Good weight percentage. Specifically, the former includes automobile parts such as instrument panels and their peripheral parts, and various home appliance parts, and the latter includes automobile bumpers and the like. Also, regarding the preferred blending ratio of component (d),
It varies depending on the use of the composition of the present invention, and for applications requiring relatively high stiffness, 35 to 15% by weight, especially 35 to 20% by weight.
30 to 5% by weight, especially for applications requiring relatively high impact resistance, especially low-temperature impact resistance.
20 to 5% by weight is good. If component (a) is less than the above range, the moldability, mechanical strength, etc. will be unsatisfactory, while if it is in excess, the rigidity will be insufficient. If component (b) or component (c) exceeds the above range, no further improvement in scratch resistance can be expected, and it is also unfavorable in terms of rigidity and heat resistance. If component (d) is less than the above range, it will lack rigidity, heat resistance, etc., while if it exceeds it, it will be undesirable due to lack of scratch resistance, moldability, appearance, etc. Furthermore, if component (e) is less than the above range, the effect of the invention will not be sufficient, while if it exceeds it, it will not only have a negative effect on mechanical strength and heat resistance, but will also be unfavorable from an economical point of view. In addition to the above-mentioned components, the composition of the present invention may contain other additional components within a range that does not significantly impair the effects of the present invention. Additional components include thermoplastic resins or thermosetting resins other than the above-mentioned resin components used in the present invention (for example, homopolymers of α-olefins such as polypropylene and polybutene, copolymers of α-olefins, α- Olefin polymer resins such as copolymers of olefin and vinyl monomers, unsaturated organic acid-modified olefin polymers such as maleic anhydride-modified polypropylene, nylon, polycarbonate, acrylonitrile-butadiene-styrene resin (ABS), polystyrene, vinyl chloride,
rubber or latex components other than those used in the present invention (e.g., polybutadiene, polyisoprene, 1,2-polybutadiene, butyl rubber, nitrile-butadiene rubber, polyisobutylene, etc.), the present invention Fillers other than those used in (e.g., mica, calcium carbonate, calcium silicate, glass fiber, clay, glass powder, magnesium carbonate, wood flour, alumina, carbon fiber, etc.), antioxidants (phenol-based, sulfur-based, etc.), Lubricants, light stabilizers, ultraviolet absorbers, antistatic agents, dispersants, copper inhibitors, neutralizing agents, blowing agents, plasticizers, antifoaming agents, flame retardants, crosslinking agents, flow improvers (e.g. various oxides), weld strength improvers (for example, various peroxides), nucleating agents, and the like. The addition of these various resins and auxiliary agents not only improves scratch resistance, physical property balance, and molded product surface characteristics (gloss, weld appearance, silver streaks, flow marks, etc.), but also improves printability, paintability, adhesion, plating performance, It is effective in improving tapping properties, moldability, kneading properties, weld strength, durability, heat resistance, weather resistance, etc. These additional components can also be added in combination. The composition of the present invention can be produced using a conventional kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll, a Brabender plastograph, or a kneader. Normally, the compound is kneaded into a pellet-like compound using an extruder, etc., and then subjected to processing. However, in special cases, the filler, propylene polymer, ethylene polymer, rubber component, and pigment are directly fed to various molding machines. It is also possible to mold the product while kneading it in a molding machine. In addition, the filler is mixed in advance at a high concentration (with pigments, rubbers, or various additives as necessary) to form a masterbatch, which is then diluted with a separate propylene polymer or the like or a propylene polymer containing rubber, filler, pigments, etc. At the same time, it can also be blended and compounded and molded. The method of molding the composition of the present invention is not particularly limited, but for those with a relatively low MFR, extrusion molding and various thermoforming methods may be used.
Injection molding is suitable for products with high That is, the effects of the present invention are exhibited in molded products regardless of the molding method used, such as extrusion molding, blow molding, injection molding, sheet molding, thermoforming, rotational molding, and lamination molding. The composition of the present invention thus obtained has a high degree of scratch resistance, which is not found in conventional filler-containing propylene polymer compositions, as well as impact strength-rigidity balance, heat deformation resistance, moldability, and printing properties. It has good surface properties, paintability, plating properties, tapping properties, and creep resistance, with no noticeable sink marks or warping, and no noticeable weld lines. EXAMPLES The present invention will be explained in more detail with reference to Examples below. The various measurement methods used here are as follows. Scratch Resistance By improving the pencil scratch test device specified in JIS-K5401, a 100 yen coin was set in the pencil set part, and a test was performed on each 35 x 50 x 2 mm while applying a load of 8 kg to the uneven surface of the coin. The rough texture of the piece (height of the protrusions on average: 0.2 mm, average area: 10 mm ² ) was rubbed on the sheet at a speed of 8 cm/sec, and the marks were visually judged as follows. The measurement temperature is 23°C. (Visual results) (Judgment) The scar is not white. Grade 1. It is slightly white. Grade 2. It is quite white. Grade 3. It is white. Grade 4. Grade 2 or higher is suitable for practical purposes. Heat deformation temperature JIS-K7207 compliant (18.5Kg/cm ² ). Izotsu impact strength Measured at 23℃ in accordance with JIS-K7110 (notched). Dupont impact strength: JIS-
Using the equipment shown in Section 6-13, 2, Method B (reference test) of K5400, the diameter of the curved part of the dart and receiving plate was measured at 23°C under the condition that the diameter of the curved part was 1/2 inch. Example Component (a) was propylene-ethylene block copolymer A (ethylene content 5% by weight, boiling xylene soluble content 9% by weight, domain average dispersion diameter 1.2μ,
MFR7g/10min), same B (ethylene content 12% by weight,
Boiling xylene soluble content 15% by weight, domain average dispersion diameter 1.7μ, MFR 2g/10 min), propylene-ethylene random copolymer (ethylene content 3% by weight, boiling xylene soluble content 4% by weight, domain average dispersion diameter
1.0μ, MFR5g/10min), component (b) is high-density polyethylene (density 0.955g/cm ³ , MFR10g/10
), medium density polyethylene (density 0.930g/cm ³ ,
MFR5g/10min), as component (c), ethylene-propylene copolymer rubber A (manufactured by Nippon Gosei Rubber Co., Ltd.,
EP07P: Propylene content 26% by weight, Mooney viscosity ML ₁₊₄ [100℃] 70), EP07P (manufactured by Japan Synthetic Rubber Co., Ltd.,
EP11: Propylene content 49% by weight, Mooney viscosity
40), as component (d), talc A (produced in China: average particle size
1.5μ, specific surface area 39500cm ² /g, particle size distribution 10μ or less98
Barium sulfate (average particle size 0.4μ), colloidal calcium carbonate (average particle size
0.2μ), calcium silicate (average particle size 6μ), component (e), blue, yellow, and red coloring components including phthalocyanine blue (average particle size 0.05μ, specific surface area 79).
m ² /g), ultramarine blue (0.25μ, 13m ² /g), isoindolinone yellow (0.12μ, 26m ² /g), medium yellow lead (0.17μ, 6m ² /g), polyazolet (0.10μ, 39
m ² /g) and iron oxide (0.10 μ, 16 m ² /g), and using aluminum stearate and magnesium stearate as dispersants, respectively, in the proportions shown in Table 1, using Super Mixer manufactured by Kawada Seisakusho. At 2
The mixture was mixed for minutes, and then kneaded and granulated at 230°C using an FCM type twin-screw extruder manufactured by Kobe Steel (a single-screw extruder manufactured by Mitsubishi Heavy Industries, Ltd. was used for products using glass fiber). Thereafter, specimens were molded at 230°C using a screw-in-line injection molding machine, and their scratch resistance, impact strength, and heat distortion temperature were evaluated. The results are shown in Table 1. All exhibited good scratch resistance and a good balance of physical properties. Next, the composition of Example 2 in Table 1 (pellet-like compound) was molded using a Mitsubishi Natco 800EXL screw in-line injection molding machine, with a width of 300 mm x length of 600 mm.
Model molded flat plates (with coarse graining) were molded, measuring 3mm x 3mm in wall thickness, assuming large automobile parts such as instrument panels, consoles, and trims, and home appliance parts such as air conditioners and televisions. The moldability and fluidity at this time were good. The molded products obtained not only have sufficient scratch resistance for automobile parts, home appliance parts, etc., but also have similar impact strength, heat deformation resistance, rigidity and weld strength, and are free from flow marks, silver streaks, and grain marks. It had a good appearance with no noticeable scratches, excellent gloss, less noticeable weld lines, less noticeable sink marks and less warpage, and good creep resistance, printability, paintability, plating and tapping properties. Comparative Example In addition to the propylene-ethylene block copolymer A, high-density polyethylene, ethylene-propylene copolymer rubber A, talc A, blue, yellow, and red coloring components and dispersant used in the examples, (a ) Propylene-ethylene block copolymer C as component
(Ethylene content 3% by weight, boiling xylene soluble content 2.5
Weight%, average dispersion diameter of domains 1.1μ, MFR10
g/10 minutes), D (6% by weight, 8% by weight, 2.5μ, respectively)
6g/10min) (d) Talc B as ingredient (produced in China:
Samples were prepared in the same manner as in Examples using Mica B (phlogopite, produced in India, with an average particle size of 12μ and a specific surface area of ^180μ ) and Mica B (phlogopite produced in India with an average particle size of 180μ). In either case, the scratch resistance did not reach a practical level or the balance of physical properties (heat deformation resistance, impact strength) was poor. In other words, the average particle size of the coloring component is more than 0.2μ or the specific surface area is less than 25m ² /g, or if they are 0.2μ or less, 25
Even if the content was m ² /g or higher, if the amount of the compound was not appropriate, the scratch resistance level did not reach a practical level. Further, the same was true for those in which the mixing ratio of the coloring component and dispersant exceeded 9.0 or less than 0.4, and the physical property balance was also poor. Propylene-ethylene copolymers with inappropriate ethylene content, boiling xylene soluble content, and domain average dispersion diameter, fillers with excessive average particle diameters, or no fillers at all are prohibited. The scratch resistance level did not reach the practical level, or even if it did, the balance of physical properties deteriorated and the practicality was not recognized.

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Claims (1)

[Claims] 1 Consisting of the following components (a) to (e), (a), (b), (c), (d)
The mixing ratio of (a) + (b) + (c) + (d) is 30 each.
~90wt%, 20~5wt%, 40~0wt% and
35 to 5% by weight, and the proportion of (e) is (a) + (b) + (c)
A filler-containing colored propylene polymer composition characterized in that the amount is 1 to 10% by weight based on +(d). (a) Propylene with an ethylene content of 2 to 15% by weight, a boiling xylene soluble content of 4 to 15% by weight, and an average dispersion diameter of domains consisting of a polyethylene portion and an amorphous propylene-ethylene copolymer portion of 2.0μ or less - Ethylene block or random copolymer (b) Ethylene polymer with a density of 0.920 g/cm ³ or more and a melt flow rate of 0.1 to 50 g/10 min (c) Propylene content of 20 to 60% by weight, Mooney viscosity
ML ₁₊₄ (100℃) 15-120 ethylene-propylene copolymer rubber (d) Talc with average particle size 0.2-5μ and talc 0.1-0.5μ
At least one filler selected from barium sulfate (e) with an average particle size of 0.2 μ or less and a specific surface area of 25 m ² /
A pigment consisting of a coloring component (A) and a dispersant (B) in which the component (g or more) occupies at least 30% by volume, and the blending ratio of (A) and (B) [○I/○B] is 0.4 to 9 by weight.