JPH09111055A - Polyolefin resin composition - Google Patents

Abstract

(57) Abstract: The composition of the present invention has high rigidity and good transparency. In addition, there is little adhesion to rolls and dies during molding and less bleeding on the surface of the molded product, and there is an advantage that stable operation can be performed for a long time. SOLUTION: (A) 100 parts by weight of a polyolefin resin, (B) 0.01 to 0.50 parts by weight of a transparent nucleating agent containing a phosphoric acid aryl ester compound represented by the formula (I) as a main component, and ( C) Fatty acid amide having 12 to 22 carbon atoms.
A polyolefin resin composition obtained by melt-kneading 003 to 0.3 parts by weight.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin, particularly a random copolymer composition of propylene and ethylene or / and butene, and more specifically, the generation of deposits on a mold or roll during molding is improved. It also relates to a polypropylene resin composition having excellent transparency.

[0002]

2. Description of the Related Art In fields where it is necessary to see contents such as sheets for daily sundries packaging and injection molded containers, polyolefin resins, especially propylene-ethylene random copolymer with good transparency are used. Polymers and propylene-ethylene-butene random copolymers (hereinafter referred to as propylene random copolymers) to which a transparent nucleating agent is added are used. As a transparent nucleating agent, talc or aluminum benzoate has insufficient transparency, and thus, a sorbitol-based or phosphorus-based transparent nucleating agent has been mainly used in recent years.

However, when the sorbitol-based nucleating agent is used alone, decomposed products or sublimates of the nucleating agent adhere to the cooling roll during extrusion molding, and if the molding is continued as it is, the adhered matters will be attached to the product and adversely affect molding. You have to stop and clean the rolls. In addition, in the case of injection molding, a problem such as clouding of the mold occurs and the surface of the product is adversely affected. Therefore, the molding must be stopped and cleaned in the same manner.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Addition of fatty acid amides, antistatic agents, various waxes and oils, etc. to reduce the amount of deposits on rolls, and to prevent the decomposition of transparent nucleating agents, strengthening antioxidants and polypropylene copolymers The method of stabilizing the catalyst residue of 1 has been taken, but none of them has yet obtained satisfactory results.

Further, 2,2-methylenebis (4,6-di-tert-butylphenyl) phosphate is used as a phosphorus-based nucleating agent.
The use of sodium [formula (II)] had a good effect of reducing the deposits on the rolls, but the melting point was very high at 400 ° C or higher, and it actually did not melt in the resin, so There has been a problem that a poor dispersion occurs and a sufficient transparency improving effect cannot be stably obtained.

[0006]

Embedded image

Further, as a transparent nucleating agent, JP-A-5-15
607 is disclosed. This contains a phosphoric acid aryl ester compound represented by the formula (I) of the present invention as a main component, and in order to improve the dispersibility of this transparent nucleating agent in a resin, an organic carboxylic acid alkali metal salt, β-dicarboxylic acid is used. At least one selected from an alkali metal salt of ketonate and an alkali metal salt of β-ketoacetic acid ester is added. However, they have a drawback that they have many deposits on the roll.

[0008]

DISCLOSURE OF THE INVENTION The present invention aims to obtain a composition which is excellent in rigidity and transparency and has less deposits on rolls and molds during molding.
(A) 100 parts by weight of polyolefin resin combination, (B)
0.01 to 0.50 parts by weight of a transparent nucleating agent containing a phosphoric acid aryl ester compound represented by the formula (I) as a main component, and (C) a fatty acid amide having 12 to 22 carbon atoms 0.003 to
By using a polyolefin resin composition obtained by melt-kneading 0.3 parts by weight, roll deposits are unlikely to occur during extrusion molding, and die deposits during injection molding can be greatly reduced, making it a transparent molded product. The present invention has been achieved by finding that

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described in detail below. The polyolefin resin (A) of the present invention is a homopolymer of an α-olefin such as ethylene or propylene, or a copolymer of ethylene, propylene or the like with another α-olefin. Specifically, they are high and low density polyethylene, ethylene-α-olefin copolymers, polypropylene, propylene-ethylene random and block copolymers and the like. Of these, a propylene random copolymer is particularly preferable. The propylene random copolymer has a propylene content of 90% by weight or more, preferably 9%.
It is a random copolymer with 2% by weight or more of ethylene and / or butene, and the melt flow rate is (230 ° C, 2.16 kg) 1 to 50 g / 10 although not particularly specified.
Fractions are preferred. Here, the reason why the propylene content is 90% by weight or more is that when the content is less than 90% by weight, the rigidity is insufficient and the surface of the molded product becomes tacky.

The compound (B) of the formula (I) of the present invention is disclosed in JP-A-5-15607. The compound of formula (I) has a smaller adhesive force between a metal generated or scattered during molding and a metal than a sorbitol-based compound, and tends to remain on the surface of a molded product rather than transfer to the surface of a roll or a mold. It has an advantage that it can be easily removed even if it is attached to a roll or a mold.

The amount of the component (B) added is 0.01 to 0.50.
If the amount is less than 0.01 part by weight, a sufficient transparency improving effect cannot be obtained, and if the amount exceeds 0.50 part by weight, the transparency improving effect is almost unchanged, and rather the surface of a sheet or a molded article is not affected. Transition occurs and transparency deteriorates. The addition amount of the component (B) here is mainly the compound represented by the formula (I), and is the amount of the compound represented by the formula (I) including a dispersant and the like. Here, the dispersant or the like is an alkali metal carboxylate, an alkali metal β-diketonate, an alkali metal β-ketoacetic acid ester, or the like.

The component (C) fatty acid amide was not sufficient in the effect of improving adhesion to rolls and molds only by the transparent nucleating agent, and addition of the fatty acid amide was very effective. The component (C) fatty acid amide having 12 to 22 carbon atoms of the present invention is preferably oleic acid amide, erucic acid amide, stearic acid amide, behenic acid amide and the like. The addition amount is 0.
003 to 0.3 parts by weight. If it is added in an amount of less than 0.003 parts by weight, the effect of improving adhesion to rolls and dies is small, and the addition amount is less than 0.
This is because if the amount exceeds 3 parts by weight, the fatty acid amide will migrate to the surface more than necessary, and conversely the transparency will deteriorate. At this time, antistatic agents and antioxidants other than fatty acid amides have no effect. Further, if the carbon number is less than 12, it is very easy to migrate to the surface, but it is not preferable because it is whitened or sticky because it appears too much on the surface, and if it exceeds 22, the migration rate to the surface of the molded product is extremely high. Since it becomes too slow, a sufficient improvement effect cannot be obtained.

In the present invention, in addition to the above compounds, if necessary, a metal soap or a synthetic hydrotalcite compound as a catalyst neutralizing agent, a phenolic antioxidant which is generally commercially available as an antioxidant, and phosphorus. 1 selected from polyhydric alcohol fatty acid ester, alkyldiethanolamine, straight chain alkyl alcohol, polyoxyethylene alkylamine fatty acid ester, polyoxyethylene alkylamine type compound, etc. as an antioxidant, sulfur antioxidant, antistatic agent A compound consisting of one or more kinds, a hindered amine light stabilizer, a weathering agent, an antifogging agent, an antiblocking agent, other transparent nucleating agent, and an inorganic filler can be added to the extent that transparency is not deteriorated. Examples and comparative examples will be shown below.

[0014]

【Example】

Example 1 As a transparent nucleating agent containing the formula (I) as a main component, with respect to 100 parts by weight of a propylene-ethylene random copolymer having a propylene content of 97% by weight and a melt flow rate of 3.0 g / 10 min. A mixture of 58% by weight of the compound represented by formula (I) and 42% by weight of lithium stearate was added with 0.10 part by weight and 0.025 part by weight of oleic acid amide, and 0.05 part by weight of calcium stearate was added as an antioxidant. 0.05 parts by weight of tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane and 0.05% by weight of tris (2,4-di-t-butylphenyl) phosphite, 0.05 wt% of polyhydric alcohol fatty acid ester was added as an antistatic agent, and granulated at a preset temperature of 240 ° C. with a 65 mmφ single screw extruder.

The set temperature 26
The state of the deposits on the roll after 1 hour when the film was formed by a T-die forming machine at 0 ° C. was visually evaluated in three stages, and the results are shown in Table 1. ×: Vigorous deposits were generated on the entire surface of the roll, Δ: Thin deposits were generated on the roll,
◯: Almost no deposits on the roll.

Regarding the haze, a sheet having a thickness of 1.6 mm formed at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. was prepared by an injection molding machine and aged in an oven at 40 ° C. for 5 days. Was measured with an NDH type haze meter manufactured by Nippon Denshoku Industries Co., Ltd., and the results are shown in Table 1.

Mechanical properties were measured by the following measuring methods, and the results are shown in Table 1. Tensile yield strength ASTM D638 Tensile elongation at break ASTM D638 Flexural modulus ASTM D790 Izod impact strength ASTM D256 Surface hardness ASTM D785 Heat distortion temperature ASTM D648

[Example 2] Molding and evaluation were carried out in the same manner as in Example 1 except that the amount of the transparent nucleating agent added in Example 1 was 0.20 parts by weight, and the results are shown in Table 1.

[Example 3] Molding and evaluation were carried out in the same manner as in Example 1 except that the amount of the transparent nucleating agent added in Example 1 was 0.40 parts by weight, and the results are shown in Table 1.

Example 4 Example 1 was repeated except that the slip agent of Example 1 was 0.050 part by weight of erucic acid amide.
Molded and evaluated in the same manner as in, and the results are shown in Table 1.

Example 5 The same molding and evaluation as in Example 1 was carried out except that the propylene-ethylene random copolymer of Example 1 had a propylene content of 96% by weight and a melt flow rate of 2.5 g / 10 minutes. The results are shown in Table 1.

[Comparative Example 1] The transparent nucleating agent of Example 1 was added in an amount of 0.20 parts by weight, and oleic acid amide was not added.
Molded and evaluated in the same manner as in Example 1 except that parts by weight were used.
The results are shown in Table 1.

[Comparative Example 2] Example 1 except that the transparent nucleating agent of Example 1 was EC-4 (0.20 parts by weight) manufactured by EC Chemical Co., Ltd. as a commercially available sorbitol transparent nucleating agent. It was similarly molded and evaluated, and the results are shown in Table 1.

[Comparative Example 3] The transparent nucleating agent of Comparative Example 1 was used as EC.
Molding and evaluation were carried out in the same manner as Comparative Example 1 except that the result was -4, and the results are shown in Table 1.

[Comparative Example 4] The transparent nucleating agent of Comparative Example 2 was molded and evaluated in the same manner as Comparative Example 2 except that the commercially available sorbitol-based transparent nucleating agent was Gelol MD manufactured by Shin Nippon Rika Co., Ltd. The results are shown in Table 1.

Comparative Example 5 Molding and evaluation were carried out in the same manner as in Example 1 except that the oleic acid amide of Example 1 was added in an amount of 0.5 part by weight, and the results are shown in Table 1.

Comparative Example 6 Molding and evaluation were carried out in the same manner as in Example 1 except that the transparent nucleating agent of Example 1 was added in an amount of 0 part by weight, and the results are shown in Table 1.

[0028]

[Table 1]

[0029]

The composition of the present invention has high rigidity and good transparency. In addition, there is little adhesion to rolls and dies during molding and less bleeding on the surface of the molded product, and there is an advantage that stable operation can be performed for a long time.

Claims (2)

[Claims] 1. A transparent resin containing (A) 100 parts by weight of a polyolefin resin, (B) a transparent nucleating agent containing a phosphoric acid aryl ester compound represented by formula (I) as a main component, and 0.01 to 0.50 parts by weight, and (C) Fatty acid amide having 12 to 22 carbon atoms.
A polyolefin resin composition obtained by melt-kneading 003 to 0.3 parts by weight. Embedded image 2. The polyolefin resin composition according to claim 1, wherein the polyolefin resin is a random copolymer of propylene having a propylene content of 90% by weight or more and ethylene and / or butene.