JPH0318661B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to reinforced poly-4-methyl-1-pentene compositions with improved mechanical, thermal and surface properties. More specifically, the present invention provides a reinforced poly-4-methyl-1-pentene composition that has significantly improved stiffness, Izod impact strength, heat distortion temperature, appearance, and color. Conventionally, in order to improve the rigidity and impact resistance of polyolefins and other thermoplastic resins, compositions containing fillers such as powdered inorganic fillers and glass fibers have been adopted. For example, compositions made by blending powdered inorganic fillers with polyolefins such as polyethylene and polypropylene generally have rigidity,
Heat denaturation temperature, etc. are improved, but impact resistance is impaired, while compositions containing glass fibers similarly improve mechanical properties such as stiffness, heat distortion temperature, and impact resistance, but the composition Not only does the surface of the molded product have a rough surface and poor appearance, but also the mechanical properties become anisotropic due to the orientation of the glass fibers that occur during melt molding, making the molded product more likely to warp. There are drawbacks. Various attempts have been made to improve the above-mentioned drawbacks of compositions containing glass fibers. For example, in Japanese Patent Application Laid-Open No. 53-50249, polyethylene,
A composition in which potassium titanate single crystal fine fibers and polyvinyl alcohol acetal fibers are blended with a polyolefin such as polypropylene has been proposed. Compositions containing mica powder have been proposed. Although all of the polyolefin compositions proposed in these prior art documents can improve the warpage caused by the anisotropy to some extent, the polyolefin compositions described in these documents generally have low heat resistance properties such as heat distortion temperature. However, it has the disadvantage that it cannot be used for molding applications in fields where heat resistance is required. As a result of searching for a polyolefin composition with excellent mechanical properties, heat resistance properties, and surface properties for molded products, the present inventors found that a specific amount of potassium titanate crystal fine fibers was added to poly4-methyl-1-pentene. It has been discovered that the blended composition satisfies the above objectives, and the present invention has been achieved. The composition of the present invention is characterized by being excellent in various properties of molded products such as mechanical properties such as rigidity and Izod impact strength, heat resistance properties such as heat distortion temperature, and surface properties such as appearance and hue. Compared to conventional compositions made of polyethylene or polypropylene mixed with inorganic fillers such as potassium titanate crystal fine fibers, it has a significantly superior heat distortion temperature, and compared to compositions containing glass fiber, it has less rough skin phenomenon and has a white color. Because of its high pigment content, it is characterized by excellent colorability with pigments, and in particular, mechanical properties can be improved even without adding polyvinyl alcohol acetal fibers or phlogopite powder as proposed in the above-mentioned prior art document. It has the characteristic that the molded product does not warp due to anisotropy. To summarize the present invention, the present invention comprises (a) poly-4-methyl-1-pentene; (b) the poly-4-methyl-1-pentene;
potassium titanate crystal fine fibers in a range of 0.1 parts by weight or more and less than 5 parts by weight per 100 parts by weight of pentene;
(c) containing a modified polyolefin grafted with an α,β-unsaturated carboxylic acid or a derivative thereof in a range of 0.05 to 20 parts by weight based on 100 parts by weight of the poly-4-methyl-1-pentene; The gist of the invention is a reinforced poly-4-methyl-1-pentene composition. Poly4-methyl- blended into the composition of the present invention
As 1-pentene (a), in addition to a homopolymer of 4-methyl-1-pentene, the main component is a 4-methyl-1-pentene component unit and a small amount of other unsaturated polymerization component units, for example, 20 mol. % or less is acceptable. The unsaturated copolymerization component units to be copolymerized include ethylene, propylene, 1-butene, 1-pentene, 3
Examples include α-olefin component units such as -methyl-1-butene, 1-hexene, 1-octene, and 1-decene. The poly-4-methyl-1
- [η] (intrinsic viscosity measured in decalin solvent at 135° C.) of pentene is usually in the range from 0.5 to 10 dl/g, preferably from 1.0 to 5.0 dl/g. The filler blended into the composition of the present invention is potassium titanate crystalline fine fiber (b). The average thickness of the potassium titanate crystal fine fibers is usually 0.1 to
3μ, preferably in the range of 0.2 to 1μ, and the average fiber length is usually in the range of 5 to 100μ, preferably 10 to 50μ. The blending ratio of the potassium titanate crystal fine fibers (b) is as follows:
It must be in the range of 0.1 parts by weight or more and less than 5 parts by weight, more preferably 0.5 parts by weight or more and less than 5 parts by weight, particularly preferably 1 or more and less than 5 parts by weight, based on 100 parts by weight of pentene (a). in range. The blending ratio of the potassium titanate crystal fine fibers is based on 100 parts by weight of poly-4-methyl-1-pentene.
If the amount is less than 0.1 part by weight, the effect of improving the mechanical properties and heat resistance properties of the molded product will not be obtained. The reinforced poly-4-methyl-1-pentene composition of the present invention comprises two essential components: the poly-4-methyl-1-pentene (a), the potassium titanate crystal fine fibers (b), and the modified polyolefin (c). Although there are cases where the composition consists only of the above-mentioned potassium titanate, other components such as various stabilizers, pigments, secondary fillers other than the above-mentioned potassium titanate, etc. can be added as necessary. Various stabilizers, pigments, etc. are blended in appropriate proportions. The reinforced poly-4-methyl-1-pentene composition of the present invention comprises two essential components: the poly-4-methyl-1-pentene (a), the potassium titanate crystal fine fibers (b), and the modified polyolefin (c). In addition, it is preferable to contain an inorganic or organic filler other than potassium titanate, since the molded article formed from the composition will have excellent rigidity and heat distortion temperature. Specifically, preferable inorganic fillers other than potassium titanate crystalline fine fibers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide,
Pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, dolomite,
Calcium sulfate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite,
Examples include graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, and aromatic polyamide fiber. Among these inorganic or organic fillers, when at least one inorganic filler selected from the group consisting of barium sulfate, calcium carbonate, talc, white mica, and glass flakes is used in combination with the potassium titanate crystalline fine fibers, is particularly preferred since the molded body formed from the composition has excellent rigidity and heat distortion temperature. The blending ratio of the inorganic or organic filler other than the potassium titanate crystal fine fibers is as follows:
Usually 0 to 150 parts by weight, preferably 2 to 100 parts by weight per 100 parts by weight, and usually 0 to 2000 parts by weight, preferably 0 to 2000 parts by weight per 100 parts by weight of the potassium titanate crystalline fine fiber (b). 5 or more
In the range of 1500 parts by weight. A composition in which modified polyolefin (c) is blended with the reinforced poly-4-methyl-1-pentene composition of the present invention is preferable because it further improves various properties such as the mechanical properties, heat resistance properties, and surface properties of the molded product. be. Here, the modified polyolefin (c) is
It is a modified polyolefin to which an α,β-unsaturated carboxylic acid or a derivative thereof such as an α,β-unsaturated carboxylic acid, its acid anhydride or its ester is grafted, especially an α,β-unsaturated dicarboxylic acid or its acid anhydride. Preferred are modified polyolefins to which polyolefins are grafted. Examples of the α,β-unsaturated carboxylic acid, its anhydride, or its ester component as a graft component include acrylic acid, methacrylic acid, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, and acrylic acid. Examples include methyl acid, methyl methacrylate, monomethyl maleate, dimethyl maleate, dimethyl citraconate, and dimethyl itaconate. As polyolefin, ethylene,
Homopolymers of α-olefins such as propylene, 1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, or two or more of these components Copolymers can be exemplified. It is particularly preferable that the modified polyolefin is modified polypropylene or modified poly-4-methyl-1-pentene, since the above-mentioned properties of the reinforced poly-4-methyl-1-pentene composition of the present invention are greatly improved. The saponification value of the modified polyolefin is 0.5 to 200mg
It is preferably in the range of KOH/1g. Also,
The blending ratio of the modified polyolefin (c) is preferably in the range of 0.05 or more and 20 parts by weight based on 100 parts by weight of the poly 4-methyl-1-pentene (a). The saponification value of the composition of (a) and the modified polyolefin (c) is usually 0.025 to 40 mgKOH/1g, preferably 0.1 to 20mg
The ratio is in the range of KOH/1g. The composition of the present invention can be prepared by dry blending a mixture of each component in a predetermined ratio, or by melt-mixing the mixture under heating conditions that melt the resin. It can also be prepared by The melt flow rate (MFR) of the composition of the present invention in a molten state is determined by a method according to ASTM-D-1238.
The value measured at a temperature of 260℃ and a load of 3000g) is normal.
0.1 to 200g/10min, preferably 1 to 200g/10min
The range is 100g/10min. The reinforced poly-4-methyl-1-pentene composition of the present invention can be used in various applications in the molding field where heat resistance is required. Next, the reinforced poly-4-methyl-1-pentene composition of the present invention will be specifically explained with reference to Examples.
The method for preparing the test pieces and the evaluation method for various properties used in the Examples and Comparative Examples are as follows. [Preparation of test piece] A composition consisting of a predetermined ratio was mixed by Henschel at 1000 rpm for 1 minute, and then heated at 280 rpm using a single screw extruder.
Composite polymer pellets were obtained by kneading and granulating at ℃. Subsequently, specimens for predetermined physical properties were molded using an injection molding machine under the following conditions. Cylinder temperature: 290℃ Injection pressure: 350Kg/cm ² Injection speed: 4.2g/sec Mold temperature: 60℃ [Evaluation method] (1) Saponification value Accurately weigh approximately 0.5g of sample into a flask,
50 c.c. of p-xylene and 150 c.c. of DMSO were added to this and dissolved by heating. Next, 25 c.c. of N/2 potassium hydroxide was added, a reflux condenser was attached, and the mixture was heated to 135°C for 1 hour. Thereafter, the mixture was cooled to room temperature, and back calibration was performed using an N/2 hydrochloric acid standard solution using phenolphthalein as an indicator. A blank test was also conducted, and the saponification value was determined using the following formula. Saponification value = 28.055 x (A-B) x F/C A: Amount of hydrochloric acid used in the blank test (cc) B: Amount of hydrochloric acid used in the main test (cc) C: Amount of sample collected (g) F: Hydrochloric acid titer Series (2) Bending test Method described in ASTM-D-790. (3) Izot impact strength: Method described in ASTM-D-256. (4) Heat distortion temperature Method described in ASTM-D-648. (5) Hue Judgment was made visually. (6) Appearance Judgment was made visually. Comparative Example 1 Poly-4-methyl-1-pentene ([η] = 2.63
dl/g) powder, tetrakis [3-(3,5-di-tert-butyl-4-
A composition is prepared by melt-kneading a mixture consisting of 6.25 g of hydroxyphenyl)propionyloxymethyl]methane (manufactured by Ciba Geigy, trade name Irganox 1010) and 1.25 g of zinc stearate as a hydrochloric acid absorbent in the above-described manner, A test piece was prepared from the composition and evaluated by the method described above.
The results are shown in Table 1. Comparative Examples 2-3 Poly 4-methyl-1 blended in the proportions listed in Table 1
- Powder of pentene ([η] = 2.63 dl/g) and potassium titanate crystal fine fiber [Otsuka Chemicals
Co., Ltd., product name Teismo-D]
2500g, Tetrakis [3-(3,
5-di-tert-butyl-4-hydroxyphenyl)
A composition is prepared by melt-kneading a mixture consisting of 6.25 g of propionyloxymethyl]methane and 1.25 g of zinc stearate as a hydrochloric acid absorbent, and a test piece is prepared from the composition,
Evaluation was performed using the method described above. The results are shown in Table 1. Example 1 Poly 4-methyl- blended in the proportions shown in Table 1
1-pentene powder and maleic anhydride grafted poly4-methyl-1-pentene powder ([η] = 1.03 dl/g, saponification value 30 mgKOH/1 g)
(saponification value 0.30mgKOH/1g)
Comparative Example 2 was carried out in the same manner as in Comparative Example 2, except that 2000 g of potassium titanate crystal fine fibers were used and the amount of potassium titanate crystal fine fibers shown in Table 1 was used. The results are shown in Table 1. Example 2 Poly4-methyl-1-pentene powder and maleic acid grafted polypropylene powder ([η] = 0.43 dl/g, saponification value
35mgKOH/1g) (saponification value
Comparative row 2 was carried out in the same manner as in comparative row 2, except that 2000 g of 0.35 mg KOH/1 g) and the amount of potassium titanate crystal fine fibers listed in Table 1 were used. The results are shown in Table 1. Comparative Examples 4-7 Poly 4-methyl-1 blended in the proportions listed in Table 1
- 2500 g of a mixture consisting of pentene ([η] = 2.63 dl/g) powder, potassium titanate crystal fine fibers (manufactured by Otsuka Chemical Co., Ltd., trade name Teismo D), and the fillers listed in Table 1 to prevent oxidation. Tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl] as an agent
A composition was prepared by adding 6.25 g of methane and 1.25 g of zinc stearate as a hydrochloric acid absorbent and melt-kneading in the method described above. A test piece was prepared from the composition and evaluated by the method described above. The results are shown in Table 1. Example 3 Poly 4-methyl- blended in the proportions shown in Table 1
1-pentene powder ([η] = 2.63 dl/g) and maleic anhydride grafted poly4-methyl-1-
A mixture consisting of pentene powder ([η] = 1.03 dl/g, saponification value 30mgKOH/1g) (saponification value
Tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl ) A composition was prepared by adding 6.25 g of propionyloxymethyl]methane and 1.25 g of zinc stearate as a hydrochloric acid absorbent and melt-kneading in the above method. A test piece was prepared from the composition and evaluated by the above method. did. The results are shown in Table 1. Comparative Examples 8-10 Table 1 instead of potassium titanate crystal fine fibers
Comparative Example 2 was carried out in the same manner as in Comparative Example 2, except that the amount of inorganic filler described in . The results are shown in Table 1. 【table】

Claims (1)

[Scope of Claims] 1 (a) poly-4-methyl-1-pentene, (b) titanic acid in a range of 0.1 parts by weight or more and less than 5 parts by weight based on 100 parts by weight of the poly-4-methyl-1-pentene. potassium crystal fine fibers, and (c) a modified polyolefin grafted with α,β-unsaturated carboxylic acid or a derivative thereof in a range of 0.05 to 20 parts by weight based on 100 parts by weight of the poly4-methyl-1-pentene; A reinforced poly-4-methyl-1-pentene composition comprising: