JP2525319B2 - Crystalline polyolefin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline polyolefin composition capable of obtaining a molded article excellent in rigidity and heat resistance. More specifically, the present invention relates to a crystalline polyolefin composition which is obtained from a crystalline polyolefin and a specific amount of biphenylylene-di-phosphonic acid, and which gives a molded article excellent in rigidity and heat resistance.

[0002]

2. Description of the Related Art Generally, crystalline polyolefins are relatively inexpensive and have excellent mechanical properties.
It is used to manufacture various molded products such as hollow molded products, films, sheets, and fibers. However, mechanical properties may not be sufficient depending on various specific uses, and there is a problem that expansion of the specific uses is limited. In particular, the rigidity surface such as rigidity and heat resistance rigidity (hereinafter, “rigid surface means rigidity and heat resistance rigidity”) is inferior to polyesters such as polystyrene, ABS resin, polyethylene terephthalate and polybutylene terephthalate. The use of crystalline polyolefin has a drawback that it may be limited in specific applications. Therefore, various nucleating agents have been conventionally used for the purpose of improving the rigidity of crystalline polyolefin. The inventors of the present invention have disclosed a polyolefin composition capable of obtaining a molded article having improved rigidity and impact resistance at low temperatures, that is, a composition obtained by blending a specific amount of an acid phosphonate having a specific structure with polyolefin. It was previously proposed as a gazette.

On the other hand, Japanese Patent Application Laid-Open No. 51-52450 discloses a specific diphosphonic acid compound or diphosphinic acid compound containing arylene diphosphonic acid as a stabilizer for polyolefin. Also, Japanese Patent Laid-Open No.
No. 7,8,772 discloses 4,4'- as a stabilizer for natural or synthetic polymeric substances composed of benzenephosphonic acid compounds.
Biphenyl-di-phosphonous acid is described.

[0004]

However, although the rigid surface of the molded product obtained from the composition obtained by blending the crystalline polyolefin with various conventionally known nucleating agents is improved to some extent, it is still not sufficiently satisfactory. . Although the rigidity of the molded product obtained from the polyolefin composition proposed in JP-A-60-181146 is improved, it is still not sufficiently satisfactory. Further, in JP-A-51-52450, a wide range of diphosphinic acid compounds or diphosphinic acid compounds are represented by the general formula as stabilizers for polyolefins. However, although the publication describes only dimethyl-1,4-phenylene-di-acid phosphonate as an arylene diphosphonic acid compound in Examples, a polyolefin composition containing biphenylylene-di-phosphonic acid was used. There is no description or suggestion of improving the rigidity of the molded article obtained from the article. Further, in the above-mentioned JP-A-47-8772, 4,4'-biphenyl-di-
Although phosphonous acid is described, nothing is said to improve the rigidity of a molded article obtained from a polyolefin composition containing 4,4′-biphenylylene-di-phosphonic acid which is an oxide thereof. There is no suggestion.

The present inventor has earnestly studied to obtain a crystalline polyolefin composition which gives a molded article having the above-mentioned problems relating to the crystalline polyolefin composition, that is, a rigid surface. As a result, the present inventor has found that a crystalline polyolefin composition comprising a crystalline polyolefin and a specific amount of biphenylylene-di-phosphonic acid is a composition that gives a molded article having an improved rigid surface, and based on this finding. Based on this, the present invention has been completed. As is clear from the above description, an object of the present invention is to provide a crystalline polyolefin composition in which the rigidity of the molded product is improved.

[0006]

The present invention has the following constitution (1). (1) A crystalline polyolefin composition comprising 100 parts by weight of a crystalline polyolefin and 0.001 to 1 part by weight of biphenylylene-di-phosphonic acid (the following formula (1)).

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The crystalline polyolefin used in the present invention is
Ethylene, propylene, butene-1, pentene-1, 4
-Methyl-pentene-1, hexene-1, octene-1
Such as a crystalline homopolymer of α-olefin, a crystalline or low crystalline random copolymer or a crystalline block copolymer of these two or more α-olefins, the above α-
Copolymer of olefin and vinyl acetate or acrylic ester, saponified product of the copolymer, copolymer of α-olefin and unsaturated silane compound, α-olefin and unsaturated carboxylic acid or anhydride thereof A copolymer, a reaction product of the copolymer and a metal ion compound, a crystalline homopolymer of the above α-olefin, a crystalline or low crystalline random copolymer or a crystalline block copolymer. Modified polyolefin modified with unsaturated carboxylic acid or its derivative, crystalline homopolymer of the above α-olefin, crystalline or low crystalline random copolymer or crystalline block copolymer modified with unsaturated silane compound Examples thereof include silane-modified polyolefins. These crystalline polyolefins can be used alone or in combination with two types. It is also possible to use a mixture of crystalline polyolefin above.

Further, various synthetic rubbers (for example, amorphous ethylene-propylene random copolymer, amorphous ethylene-propylene-nonconjugated diene terpolymer, polybutadiene, polyisoprene, polychloroprene) are added to the above-mentioned crystalline polyolefin. , Chlorinated polyethylene, chlorinated polypropylene, fluororubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-
Butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resin (for example, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate) , Polybutylene terephthalate, polycarbonate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, fluororesin, petroleum resin (for example, C ₅ petroleum resin, hydrogenated C ₅
Petroleum resin, C ₉ petroleum resin, hydrogenated C ₉ petroleum resin, C
_5- C ₉ copolymerized petroleum resin, hydrogenated C ₅ -C ₉ copolymerized petroleum resin,
Acid-modified C ₉ petroleum resin, DCPD resin (for example, cyclopentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, cyclopentadiene-C ₅ copolymer petroleum resin, hydrogenated cyclopentadiene-C ₅ copolymer petroleum resin, Cyclopentadiene-C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₉ copolymerized petroleum resin, cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-
It is also possible to use a mixture of a C ₅ -C ₉ copolymerized petroleum resin and the like having a softening point of 80 to 200 ° C.). Crystalline propylene homopolymer, crystalline propylene copolymer containing 70% by weight or more of propylene component, which is a crystalline ethylene-propylene random copolymer, crystalline propylene-butene-1 random copolymer, crystalline An ethylene-propylene-butene-1 terpolymer, a crystalline propylene-hexene-butene-1 terpolymer and a mixture of two or more thereof are particularly preferably used.

Biphenylene di-diamine used in the present invention
As phosphonic acid (hereinafter referred to as compound A),
4,4'-biphenylylene-di-phosphonic acid, 4,3'-biphenylylene-di-phosphonic acid, 3,3'-biphenylylene-di-phosphonic acid and the like can be exemplified, especially 4,4'-
Biphenylylene-di-phosphonic acid is preferred. These compounds A may be used alone or in combination of two or more kinds. These compounds A are, for example, biphenyl-di-, such as 4,4'-biphenyl-di-phosphonous acid described in JP-A-47-8772.
Oxidize phosphonous acid or tetrakis (2,
4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3'-biphenylene-di-phosphonite or It can be obtained by hydrolyzing and oxidizing tetrakis (2,4-di-t-butylphenyl) -3,3'-biphenylene-di-phosphonite. The content ratio of the compound A is 0.00 based on 100 parts by weight of the crystalline polyolefin.
It is 1 to 1 part by weight, preferably 0.01 to 0.5 part by weight. 0.
If the content is less than 001 parts by weight, the effect of improving the rigidity cannot be fully exerted, and if it exceeds 1 part by weight, further improvement in the effect of the rigidity cannot be expected and it is not practical. It is also uneconomical.

In the composition of the present invention, various additives which are usually added to crystalline polyolefins such as antioxidants such as phenol type, thioether type and phosphorus type (excluding compound A), light stability Agent, heavy metal deactivator (copper damage inhibitor), clarifying agent, nucleating agent (however, compound A
), Lubricants, antistatic agents, antifogging agents, antiblocking agents, non-dripping agents, radical generators such as peroxides, flame retardants, flame retardant auxiliaries, pigments, halogen scavengers, metal soaps, etc. Dispersant or neutralizer, organic or inorganic antibacterial agent,
Inorganic fillers (eg talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate,
Aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, barium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite and metal Fiber etc.),
Coupling agent (for example, silane, titanate, boron, aluminate, zircoaluminate, etc.)
The above-mentioned inorganic filler or organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) which has been surface-treated with a surface-treating agent such as the above can be used in combination within the range not impairing the object of the present invention.

In the composition of the present invention, for example, a predetermined amount of each of the above-mentioned compound A added to crystalline polyolefin and the above-mentioned various additives usually added to crystalline polyolefin is used in a conventional mixing device such as a Henschel mixer (trade name), Mix using a super mixer, ribbon blender, Banbury mixer, etc., and melt kneading temperature with ordinary single-screw extruder, twin-screw extruder, Brabender or roll etc. 150 ℃ ～ 300 ℃, preferably 180 ℃ ～ 270 ℃ It can be obtained by melt-kneading and pelletizing. The obtained composition is used for production of a target molded article by various molding methods such as an injection molding method, an extrusion molding method, and a blow molding method.

[0012]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows. 1) Rigidity: Evaluated by a bending test. That is, using the pellets obtained, a test piece having a length of 100 mm, a width of 10 mm and a thickness of 4 mm was prepared by an injection molding method, and the flexural modulus was measured using the test piece (according to JIS K 7203) to obtain rigidity. Was evaluated. A material having a high rigidity means a material having a large flexural modulus. 2) Heat resistance rigidity: Evaluated by a deflection temperature under load test. That is, using the pellets obtained, length 130 mm, width 13 mm,
A test piece having a thickness of 6.5 mm was prepared by an injection molding method, and the heat distortion temperature was evaluated by measuring the heat distortion temperature (according to JIS K 7207; 4.6 kgf / cm ² load) using the test piece. A material having high heat resistance and rigidity means a material having a high heat distortion temperature. 3) Impact resistance: evaluated by the Izod impact test. That is, using the obtained pellets length 63.5 mm, width 13 mm,
A 3.5 mm-thick test piece (having a notch) was prepared by an injection molding method, and the Izod impact strength at 23 ° C. was measured using this test piece (in accordance with JIS K 7110) to evaluate the impact resistance. A material having excellent impact resistance means a material having a high Izod impact strength.

Examples 1 to 4, Comparative Examples 1 to 4 MFR as crystalline polyolefin (amount of molten resin discharged for 10 minutes when a load of 2.16 kg at 230 ° C. is applied) 6.
To 100 parts by weight of an unstabilized powdery crystalline propylene homopolymer of 0 g / 10 min, 4,4'-biphenylylene-di-phosphonic acid as the compound A, 4,3'-biphenylylene-di-phosphonic acid was added. Acid or 3,3'-biphenylylene-
A predetermined amount of each of di-phosphonic acid and other additives was placed in a Henschel mixer (trade name) at the content ratios shown in Table 1 below, and the mixture was stirred and mixed for 3 minutes, and then the caliber was 30 mm.
It was melt-kneaded at 200 ° C. with a twin-screw extruder to produce pellets. Further, as Comparative Examples 1 to 4, powdery crystalline propylene homopolymers having an MFR of 6.0 g / 10 min and not stabilized 10
A predetermined amount of each of the additives shown in Table 1 to be described later was added to 0 part by weight, and the mixture was melt-kneaded in accordance with Examples 1 to 4 to obtain pellets. The test pieces used for the evaluation of rigidity and heat resistance were obtained by pelletizing the pellets at a resin temperature of 250 ° C and a mold temperature of 50.
Prepared by injection molding at ° C. Using the obtained test piece, the rigidity and the heat resistance rigidity were evaluated by the above-mentioned test methods. The results are shown in Table 1.

Examples 5-8, Comparative Examples 5-8 Unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) as MFR 4.0 g / 10 min as crystalline polyolefin 100 In parts by weight, as compound A, 4,4'-biphenylylene-di-phosphonic acid, 4,3'-biphenylylene-di-phosphonic acid or 3,3'-biphenylylene-di-phosphonic acid and other additives Put the specified amount of each of them into the Henschel mixer (trade name) at the content ratios shown in Table 2 below, and 3
After stirring and mixing for 1 minute, use a twin screw extruder with a diameter of 30 mm to 200 ℃
Was melt-kneaded and pelletized. Comparative Examples 5 to 5
No. 8 was added to 100 parts by weight of an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) having an MFR of 4.0 g / 10 min. A fixed amount was compounded and melt-kneaded according to Examples 5 to 8 to obtain pellets. Test pieces used for evaluation of rigidity, heat resistance and impact resistance were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The obtained test pieces were used to evaluate the rigidity, heat resistance and impact resistance by the above-mentioned test methods. Table 2 shows the results.

Examples 9 to 12 and Comparative Examples 9 to 12 As crystalline polyolefin, MFR 7.0 g / 10 min, unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) 90 % And MI (amount of molten resin discharged at a load of 2.16 kg at 190 ° C for 10 minutes) 15.0 g / 10 minutes unstabilized powdered Ziegler-Natta high density ethylene homopolymer 10% by weight %, 4,4'-biphenylylene-di-phosphonic acid as compound A, 4,3 '
-Biphenylene-di-phosphonic acid or 3,3'-
A predetermined amount of each of biphenylylene-di-phosphonic acid and other additives was placed in a Henschel mixer (trade name) at a content ratio shown in Table 3 below, and the mixture was stirred and mixed for 3 minutes, and then a twin-screw extruder having a diameter of 30 mm. The mixture was melt-kneaded at 200 ° C. and pelletized. Also, as Comparative Examples 9 to 12, MFR
Is 7.0g / 10min unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5
90% by weight and MI of 15.0 g / 10 minutes and 10% by weight of unstabilized powdered Ziegler-Natta high density ethylene homopolymer in total 100 parts by weight shown in Table 3 below. A predetermined amount of each additive was blended and melt-kneaded according to Examples 9 to 12 to obtain pellets. Test pieces used for evaluation of rigidity and heat resistance rigidity were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. Using the obtained test piece, the rigidity and the heat resistance rigidity were evaluated by the above-mentioned test methods. The results are shown in Table 3.

The compounds and additives relating to the present invention shown in Tables 1 to 3 are as follows. Compound A [1]: 4,4′-biphenylylene-di-phosphonic acid Compound A [2]: 4,3′-biphenylylene-di-phosphonic acid Compound A [3]: 3,3′-biphenylylene-di -Phosphonic acid Phenolic antioxidant 1: 2,6-di-t-butyl-p-cresol Phenolic antioxidant 2: Tetrakis [methylene-3-
(3 ', 5'-Di-t-butyl-4'-hydroxyphenyl) propionate] methane phosphorus antioxidant 1: bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite phosphorus -Based antioxidant 2: bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite Ca-St: calcium stearate acid phosphonate: 10-hydroxy-9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide [manufactured by Sanko Chemical Co., Ltd .; CA] arylene diphosphonic acid: dimethyl-1,4-phenylene-di-acid phosphonate arylene diphosphonate Acid: 4,4'-biphenyl-di-phosphonous acid

[0017]

[Table 1]

The examples and comparative examples shown in Table 1 are the cases where a crystalline propylene homopolymer was used as the crystalline polyolefin. As can be seen from Table 1, Examples 1 to 1
4 contains the compound A according to the present invention,
Examples 1 to 4 and Comparative Example 1 (without compound A)
In comparison with the above, it can be seen that Examples 1 to 4 have remarkably excellent rigidity. Also, instead of the compound A, Comparative Example 2 and Example 1 in which an acid phosphonate proposed by the present inventor in JP-A-60-181146 was contained.
Comparing Nos. 4 to 4, Comparative Example 2 has an effect of improving the rigidity as compared with Comparative Example 1, but is still insufficient. Further, instead of the compound A, JP-A-51-52450
Comparative Examples 3 to 4 and Example 1 containing the arylenediphosphonic acid disclosed in Japanese Patent Publication No. 47-8772 or the arylenediphosphonic acid disclosed in Japanese Patent Publication No. 47877/1972.
Comparing Nos. 4 to 4, it can be seen that Comparative Examples 3 to 4 have almost no effect of improving the rigidity as compared with Comparative Example 1. Therefore, it is clear that the comparative examples that do not satisfy the requirements of the compound A according to the present invention do not exhibit the effects of the present invention. That is, it can be said that the rigid surface obtained in the present invention is a unique effect that can be seen only when the crystalline polyolefin contains the compound A.

[0019]

[Table 2]

Table 2 shows that a crystalline ethylene-propylene block copolymer was used as the crystalline polyolefin, and the same effects as those described above were confirmed for these. In addition, in each of the examples of the composition of the present invention shown in Table 2, the inclusion of the compound A did not cause a decrease in the impact resistance due to the improvement of the rigidity, and the impact resistance was lower than that of each comparative example. It was confirmed that there was no difference.

[0021]

[Table 3]

Table 3 shows a mixture of a crystalline ethylene-propylene random copolymer and a high-density ethylene homopolymer as the crystalline polyolefin, and the same effects as those described above were confirmed for these.

[0023]

EFFECTS OF THE INVENTION The composition of the present invention (1) is extremely excellent in the rigidity of the molded product when it is formed into a molded product. (2) Not only can it contribute to resource saving by reducing the wall thickness of the molded product, but also because the cooling speed during molding is faster, the molding speed per unit time can be increased, which also contributes to improved productivity. it can.

Claims (1)

(57) [Claims] 1. 100 parts by weight of crystalline polyolefin and 0.001-1 of biphenylylene-di-phosphonic acid
A crystalline polyolefin composition comprising parts by weight (the following formula (1)). Embedded image