JPH0242377B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to thermoplastic resin compositions containing inorganic fillers. More specifically, the present invention relates to an inorganic filler-containing thermoplastic resin composition whose main components are polypropylene and thermoplastic polyester, which have excellent rigidity, heat resistance, and impact resistance. Polyprolene containing inorganic fillers, especially glass fiber-reinforced polypropylene (hereinafter sometimes referred to as FR-PP), has superior heat resistance and rigidity compared to ordinary crystalline polypropylene, so it is used as an engineering plastic for industrial use. It is used by being molded into parts, electrical appliance parts, automobile parts, and sports and leisure equipment. However, it has lower impact resistance than glass fiber-reinforced engineering plastics, such as glass fiber-reinforced nylon and polycarbonate, so it has not been used much in fields where impact resistance is particularly required. On the other hand, thermoplastic polyester containing inorganic filler,
Among them, glass fiber-reinforced thermoplastic polyester (hereinafter sometimes referred to as FR-PES) has a high heat distortion temperature and good electrical properties, so it is widely used in light electrical parts. However, FR-PES has drawbacks such as poor hot water resistance and poor impact strength. Attempts to improve heat-resistant rigidity and hot water resistance by mixing FR-PP and FR-PES have been proposed in Japanese Patent Publication No. 57-57499 or Japanese Patent Application Laid-open No. 120949-1982, etc. However, since the compatibility between polypropylene and thermoplastic polyester is extremely poor, the impact strength of the above mixture cannot be said to be as excellent as shown above. Therefore, as a result of intensive studies to improve the impact resistance of a composition consisting of polypropylene, thermoplastic polyester, and inorganic filler, it was found that a specific modified ethylene/α-olefin copolymer may be added to the above composition. This is what led to the discovery of the present invention. That is, the present invention provides crystalline propylene polymers.
(A), plastic polyester (B), modified ethylene α-
In a composition consisting of an olefin copolymer (C) and an inorganic filler (D), the modified ethylene/α-olefin copolymer (C) has a crystallinity of 0 or 0 when measured by X-rays.
50% by weight and ethylene content 50 to 93 mol%
The ethylene/α-olefin copolymer (E) is graft-modified with 0.01 to 5% by weight of a graft monomer selected from unsaturated carboxylic acids or derivatives thereof, and is the sum of components (A) and (B). Component (C) is 1 to 80 parts by weight per 100 parts by weight, and (D)
A thermoplastic resin composition containing an inorganic filler, characterized in that the component is contained in an amount of 5 to 150 parts by weight.
The propylene polymer (A) used in the present invention is crystalline and preferably has a density of 0.89 to 0.93.
g/cm ³ , melt flow rate (MFR: ASTM
D 1238, L) is 0.01 to 50g/10min, and is a propylene homopolymer or a combination of propylene and a small amount of α-olefin such as ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, etc. It is a block or random copolymer. The crystalline propylene polymer (A) used in the present invention is usually a graft monomer partially or wholly selected from unsaturated carboxylic acids or derivatives thereof.
It is preferable to use a graft-modified propylene polymer in an amount of 0.001 to 10% by weight, preferably 0.1 to 5% by weight, since the effect of improving impact resistance and the like is further excellent. The thermoplastic polyester (B) used in the present invention includes ethylene glycol, propylene glycol, 1,
4-butanediol, neopentyl glycol,
Aliphatic glycol such as hexamethylene glycol, alicyclic glycol such as cyclohexanedimethanol, aromatic dihydroxy compound such as bisphenol, or a dihydroxy compound unit selected from two or more of these, and terephthalic acid, isophthalic acid, 2 , aromatic dicarboxylic acids such as 6-naphthalene dicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, undecadicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, or these. A polyester formed from dicarboxylic acid units selected from two or more of the following, as long as it exhibits thermoplasticity:
It may be modified with a polyhydroxy compound, polycarboxylic acid, or the like having a higher value than the polyhydric acid. Specifically, these thermoplastic polyesters include polyethylene terephthalate, polybutylene terephthalate,
Examples include polyethylene isophthalate/terephthalate copolymer. The modified ethylene/α-olefin copolymer (C) used in the present invention has a crystallinity of 0 to 50 by X-rays.
%, preferably 0 to 30% and an ethylene content of 50 to 93 mol%, preferably 70 to 90 mol%, selected from unsaturated carboxylic acids or derivatives thereof. It is a copolymer graft-modified with 0.01 to 5% by weight, preferably 0.1 to 1.0% by weight of a graft monomer. Even if a graft-modified copolymer of ethylene/α-olefin copolymer (E) with a crystallinity of 50% and an ethylene content of more than 93 mol% is used, the impact resistance of the polymer composition is almost negligible. Not improved. In addition, the ethylene/α-olefin copolymer (E)
is usually the melt flow rate (MFR: ASTM D
1238, L) is 0.05 to 50g/10min, and
A range of 0.5 to 20 g/10 min is preferable.
If a copolymer with MFR outside the above range is used,
Modified ethylene/α-olefin copolymer (C) obtained from the copolymer and the modified propylene copolymer
The difference in melt viscosity between polyester (A) and thermoplastic polyester (B) tends to increase, the dispersion effect is not sufficient, and the effect of improving impact resistance is not sufficient. The α-olefin component unit constituting the ethylene-α-olefin copolymer (E) has 3 carbon atoms.
The above are α-olefins of about 3 to 18 in particular, such as propylene, 1-butene, 1-hexene,
Examples include 4-methyl-1-pentene and 1-decene, and they are one kind or a mixture of two or more kinds thereof. The ethylene-α-olefin copolymer is usually a copolymer of an ethylene component and an α-olefin, but in some cases it may contain a trace amount, for example, 0.5 mol% or less, of a diene component. can not use. As unsaturated carboxylic acids or derivatives thereof,
Acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocys-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid) ), or derivatives thereof, such as acid halides, amides, imides, anhydrides, esters, etc.
Specifically, maleyl chloride, maleimide, maleic anhydride, methyl acrylate, methyl methacrylate, citraconic anhydride, monomethyl maleate,
Examples include dimethyl maleate and glycidyl maleate. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are particularly preferred. To produce the modified ethylene/α-olefin copolymer (C) by graft copolymerizing the graft monomer selected from the unsaturated carboxylic acids or derivatives thereof to the ethylene/α-olefin copolymer (E), Various conventionally known methods can be employed. For example, there is a method of melting the ethylene/α-olefin copolymer (E) and adding a graft monomer to carry out graft copolymerization, or a method of dissolving the ethylene/α-olefin copolymer (E) and adding a graft monomer to carry out graft copolymerization. In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator. Grafting reaction is usually 60 to 350
It is carried out at a temperature of °C. The proportion of the radical initiator used is usually in the range of 0.001 to 1 part by weight per 100 parts by weight of the ethylene/α-olefin copolymer.
As radical initiators organic peroxides, organic peresters such as benzoyl peroxide,
Dichlorobenzoyl oxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-
Dimethyl-2,5-di(peroxide benzoate) hexyne-3,1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-
2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, Cumyl perpivalate and tert-butyl perdiethyl acetate, as well as other azo compounds such as azobisisobutyronitrile, dimethylazoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxy)
Hexyne-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,4-
Dialkyl peroxides such as bis(tert-butylperoxyisopropyl)benzene are preferred. The inorganic filler (D) in the present invention refers to powder fillers, such as alumina, magnesium oxide, calcium oxide, oxides such as zinc white, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, Hydrated metal oxides such as tin oxide hydrate, zirconium oxide hydrate, etc.;
Carbonates such as calcium carbonate, magnesium carbonate etc.; silicates such as talc, clay, bentonite, attapulgite etc.; borates such as barium borate, zinc borate etc., aluminum phosphate, sodium tripolyphosphate etc. phosphates such as; sulfates such as gypsum; sulfites; and mixtures of two or more thereof; fibrous fillers such as glass fibers, potassium titanate fibers;
Metal-coated glass fibers, ceramic fibers, wollastonite, carbon fibers, metal carbide fibers, cured metal fibers, etc., as well as spherical objects such as glass beads, glass balloons, and glass balloons, glass powder,
Examples include glass flakes and mica. Further, the surface of the inorganic filler may be treated with a silane compound such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, etc. Among these, fibrous materials, especially glass fibers, are preferred because they have excellent reinforcing effects. The inorganic filler-containing thermoplastic resin composition of the present invention contains 95 to 5 parts by weight, preferably 90 to 60 parts by weight of the above-mentioned crystalline propylene polymer (A), and 5 to 95 parts by weight of the thermoplastic polyester (B). parts, preferably 10 to 40 parts by weight (the total of both components is selected to be 100 parts by weight) and the modified ethylene/α-olefin copolymer per 100 parts by weight of the total amount of both components.
(C) is 1 to 80 parts by weight, preferably 10 to 40 parts by weight, and inorganic filler (D) is 5 to 150 parts by weight,
It preferably comprises 10 to 100 parts by weight.
If the crystalline propylene polymer (A) is less than 5 parts by weight, the effect of improving hot water resistance due to the addition of the propylene polymer will not be achieved, while if it exceeds 95 parts by weight, the heat resistance, rigidity, and paintability of the thermoplastic polyester (B) will be reduced. , there is no improvement in oil resistance, etc. If the modified ethylene/α-olefin copolymer (C) is less than 1 part by weight, the impact resistance of the composition will not be improved, and if it exceeds 80 parts by weight, the rigidity, heat resistance, oil resistance, surface hardness, etc. of the composition will be affected. There is a large decrease in If the inorganic filler (D) is less than 5 parts by weight, the rigidity, heat resistance, etc. of the composition will not be improved, and if it exceeds 150 parts by weight, disadvantages such as poor melt flowability and poor appearance of the composition will become noticeable. Become. In order to obtain the inorganic filler-containing thermoplastic resin composition of the present invention, the propylene polymer (A), the thermoplastic polyester (B), the modified ethylene/α-olefin copolymer (C), and the inorganic filler ( D) is mixed using various known methods within the above range, such as a Henschel mixer, V-blender, ribbon blender, tumbler blender, etc., and then melt-kneaded using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, etc. to produce the product. A method of granulating or crushing can be adopted. The composition of the present invention may contain heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, engraving agents, flame retardants, pigments or dyes, other polymers, etc. within the range that does not impair the purpose of the present invention. It may be mixed in advance. The characteristic feature of the inorganic filler-containing thermoplastic resin composition of the present invention is that in order to improve the dispersion of the thermoplastic polyester into the propylene polymer and the compatibility with the inorganic filler, the above-described specific modified ethylene/α-olefin is added. By adding the copolymer, the effect of modifying the propylene polymer by the thermoplastic polyester and the inorganic filler is fully exhibited, and the impact resistance of the composition is significantly improved. The inorganic filler-containing thermoplastic resin composition of the present invention has extremely superior impact resistance compared to conventionally known inorganic filler-containing polypropylene, and maintains high levels of rigidity, heat resistance, surface hardness, etc. As described above, since the composition of the present invention has both rigidity and impact resistance, it can be used in fields where FR-polyamide, FR-polycarbonate, etc. have been conventionally used, such as automobile parts, such as air cleaner housings, etc. It is suitable for various uses such as cooling fans, tuners, seat bags, etc., and electrical parts such as power tool housings, motor fans, connectors, motor covers, and coil bobbins. Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded. The measurement method used in the examples of the present invention is as follows. Tensile properties ASTM D 638 Bending properties ASTM D 790 Izot impact strength ASTM D 256 Notched heat distortion temperature ASTM D 648 Load 18.6Kg/
Production example of ^cm2 modified ethylene/α-olefin random copolymer Ethylene content 80 mol%, crystallinity 5%,
100 parts by weight of ethylene-propylene random copolymer (hereinafter referred to as EPC-1) with an MFR of 1.2g/10min, 1.0 parts by weight of acetone, 0.02 parts by weight of α,α-bis-tert-butylperoxy-diisopropylbenzene, and maleic anhydride. A mixed solution consisting of 1.0 parts by weight was mixed dropwise in a Henschel mixer, and then granulated at 240°C in a 40 mmφ extruder to obtain a crystallinity of 3%.
MFR0.8g/10min, maleic anhydride grafted ethylene/propylene random copolymer (modified EPC-
1) was obtained. Example 1 Polypropylene with MFR of 10g/10min (hereinafter
PP-1) 72 parts by weight, MFR16g/10min,
3 parts by weight of modified polypropylene (hereinafter referred to as modified PP) with a maleic anhydride grafting amount of 3.8% by weight, o
-25 parts by weight of polybutylene terephthalate (hereinafter referred to as PBT) with an intrinsic viscosity [η] of 0.65 dl/g measured at 25°C in a chlorophenol solution, modified
After dry blending 15 parts by weight of EPC-1 and 30 parts by weight of glass fiber with a length of 3 mm (hereinafter referred to as GF) in a tumbler blender, 240 parts by weight in a 40 mmφ extruder
Pellets were produced by granulation at °C. The pellets were dried and then injection molded at 260°C to prepare test pieces for measuring physical properties. The results are shown in Table 1. Examples 2 to 4 The same procedure as in Example 1 was conducted except that the quantitative ratios of PP-1, PBT, and modified EPC-1 were changed as shown in Table 1. The results are shown in Table 1. Comparative Example 1 The same procedure as in Example 1 was carried out except that modified EPC-1 was not used. The results are shown in Table 1. Comparative Example 2 In Example 1, EPC was used instead of modified EPC-1.
The same procedure as in Example 1 was carried out except that -1 was used. The results are shown in Table 1. Example 5 The same procedure as in Example 1 was carried out except that PP-1 was used instead of modified PP. The results are shown in Table 1. Comparative Example 3 In Example 1, except that instead of modified EPC-1, high-density polyethylene with a crystallinity of 74% and an MFR of 5.5 g/10 min grafted with 0.3% by weight of maleic anhydride (hereinafter referred to as modified PE) was used. was carried out in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 4 In Example 1, ethylene/methacrylic acid copolymer (MFR12g/
10min ASTM D 1238, E, ethylene content
The same procedure as in Example 1 was conducted except that 88% by weight (hereinafter referred to as EMA) was used. The results are shown in Table 1.

[Table] Example 6, Comparative Example 5 In Example 1 and Comparative Example 1, mica (susolite mica, 200 mesh pass) was used instead of GF.
The same procedure as in Example 1 and Comparative Example 1 was carried out except that . The results are shown in Table 2. Example 7, Comparative Example 6 Example 1 and Comparative Example 1 except that talc (average particle size 4μ) is used instead of GF.
The same procedure as in Comparative Example 1 was carried out. The results are shown in Table 2.

【table】

Claims (1)

[Claims] 1 In a composition consisting of a crystalline propylene polymer (A), a thermoplastic polyester (B), a modified ethylene/α-olefin copolymer (C), and an inorganic filler (D), the modified ethylene/α-olefin copolymer Polymer (C)
is ethylene α with an X-ray crystallinity of 0 to 50% by weight and an ethylene content of 50 to 93 mol%.
- Adding a graft monomer selected from unsaturated carboxylic acids or derivatives thereof to the olefin copolymer (E)
It is graft modified by 0.01 to 5% by weight, and (C) is added to 100 parts by weight of the total amount of components (A) and (B).
Component is 1 to 80 parts by weight, and component (D) is 5 to 80 parts by weight.
A thermoplastic resin composition containing an inorganic filler in an amount of 150 parts by weight.