JPH09262891A - Propylene resin extrusion-molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress an instrumental pollution at extrusion molding and improve the transparency of resin by a method wherein the specified ratios of metal salt of rosin, tertiary amine type light stabilizer and aromatic phosphite and/or aromatic phosphonite-based anti-oxidant are moxed to propylene resin. SOLUTION: To 100 pts.wt. of propylene resin, 0.03-2 pts.wt. of metal salt of rosin, 0.01-1 pts.wt. of tertiary amine type light stabilizer and 0.01-0.5 pts.wt. of aromatic phosphite and/or aromatic phosphonite anti-oxidant the blended in order to get a resin composition by means of a mixer and a kneader normally used. As the propylene resin, one having the melt flow rate of 0.1-50g/10min is suitable from the view point of the fluidity at extrusion molding and the mechanical strength of a body. Thus, an instrumental pollution can be suppressed at extrusion molding and, at the same time, the transparency of the resin, its hue and its heat aging resistance are improved.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is directed to the suppression of equipment contamination during extrusion molding by the addition of a specific additive, and to the transparency,
The present invention relates to a propylene resin extruded product having excellent hue and heat aging resistance.

[0002]

2. Description of the Related Art Polypropylene is excellent in moldability, rigidity, luster and the like, and is also excellent in hygiene and heat resistance. Therefore, it is subjected to various molding processes, and other resins such as polyvinyl chloride and polystyrene are used. It is also used in a wide range of applications such as industrial parts, daily necessities, food containers, etc. Since polypropylene is crystalline, it is superior in heat resistance to polyvinyl chloride and polystyrene, and therefore its range of use is expanding. However, polypropylene has a drawback that it is inferior in transparency as compared with polyvinyl chloride and polystyrene due to its crystallinity. Especially in sheet molding, hollow molding, extrusion molding such as film molding,
Since the melt-extruded polypropylene has a slow cooling rate, crystals grow and the transparency is further deteriorated.

In order to improve the transparency of polypropylene, there is a method of blending various nucleating agents. As the nucleating agent, inorganic powder, aromatic carboxylic acid metal salt, aromatic phosphoric acid metal salt and sorbitol derivative are used. Etc. are generally known. Among these nucleating agents, those containing a sorbitol derivative are the most transparent, but in extrusion molding, the sorbitol derivative sublimes during molding and contaminates equipment such as molding machines and cooling rolls. And the problem of generating odor are not preferred. On the other hand, a nucleating agent such as an inorganic powder, a metal salt of an aromatic carboxylic acid, a metal salt of an aromatic phosphoric acid or the like is insufficient in the effect of improving transparency.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to improve the drawbacks of the prior art and to provide a propylene resin extruded product which is excellent in transparency while suppressing equipment contamination during extrusion molding of propylene resin. To provide.

[0005]

Means for Solving the Problems The inventors of the present invention have made earnest studies to solve the above problems, and as a result, the above objects have been achieved by blending specific additives, and in addition, the hue and heat aging resistance have been improved. The present invention has been completed by finding that an excellent extruded product can be obtained.

That is, the present invention relates to a propylene resin 10
0 parts by weight, metal salt of rosin 0.03 to 2 parts by weight, tertiary amine type light stabilizer 0.01 to 1 part by weight, and aromatic phosphite and / or aromatic phosphonite antioxidant It is a propylene resin extruded product characterized by comprising 0.01 to 0.5 part by weight of the agent.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The propylene resin used in the present invention is a homopolymer of propylene or a copolymer of propylene containing propylene as a main component and another polymerizable monomer. It is manufactured by a legal method or a copolymerization method. Here, as the polymerizable monomer, α-olefin (ethylene, butene, pentene, hexene, octene, decene, 3-methylbutene, 4-methylpentene, etc.), unsaturated carboxylic acid or its derivative (acrylic acid, acrylic acid) Methyl acid, ethyl acrylate, maleic anhydride, etc.), vinyl esters (vinyl acetate, vinyl butyrate, etc.), unsaturated aromatic monomers (styrene, α-methylstyrene, etc.), and the like. Any of copolymerization forms such as block, random, and graft may be used.

This propylene resin is JIS-K675.
8 (230 ° C., 2.16 kg load) has a melt flow rate (MFR) of 0.1 to 50 g / 1.
0 minutes, especially 0.2 to 30 g / 10 minutes, especially 0.4 to 2
It is preferably 0 g / 10 minutes from the viewpoint of fluidity and mechanical strength during extrusion molding. Such a propylene resin can be appropriately selected and used from commercial products.

The metal salt of rosin used in the present invention is preferably a metal salt whose metal type is alkali metal, alkaline earth metal, aluminum, zinc or the like. Among them, metal salts of lithium, potassium, sodium, calcium, magnesium, aluminum and zinc are preferable, and metal salts of lithium, potassium and sodium are particularly preferable. As the rosin, any of a saturated type, an unsaturated type and a mixture thereof may be used. These may be used in combination and usually a mixture is often used.

Further, as the tertiary amine type light stabilizer used in the present invention, the following compounds [1] to [6] can be preferably mentioned. [1] Polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine [2] Tetrakis (1,2,2,6,6) -Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate [3] Tris (1,2,2,6,6-pentamethyl-
4-piperidyl) -dodecyl-1,2,3,4-butanetetracarboxylate [4] N, N-bis (3-aminopropyl) ethylenediamine.2,4-bis [N-butyl-N- (1, Two
2,6,6-Pentamethyl-4-piperidyl) amino]
-6-Chloro-1,3,5-triazine condensate [5] 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyrimalonic acid bis (1,
2,2,6,6-Pentamethyl-4-piperidyl) ester [6] Bis (1,2,2,6,6-pentamethyl-4)
-Piperidyl) sebacate Among the tertiary amine type light stabilizers, the molecular weight is 500 in particular.
The above are preferable because they can exhibit compatibility and excellent heat aging resistance. The most suitable compounds are the above-mentioned compounds [1], [2], [3] and [4].

Further, as the aromatic phosphite ester and / or aromatic phosphonite type antioxidant used in the present invention, for example, the following compounds [7] to [18] are preferable. it can. [7] Tris (2,4-di-t-butylphenyl) phosphite [8] Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-di-phosphonite

[9] Tris (mixed, mono and dinonylphenyl) phosphite [10] Methylenebis (4,6-di-t-butylphenyl) -2-ethylhexyl phosphite [11] Tris-nonylphenyl phosphite [12] Tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite [13] 4,4'-butylidene bis (3-methyl-6-
t-Butylphenyl-di-tridecyl) phosphite [14] 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane [15] bis (2,2 4-Di-t-butylphenyl) pentaerythritol-di-phosphite [16] Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite [17] 2,2 ' -Ethylidene bis (4,6-di-t-
Butylphenyl) fluorophosphite [18] Bis (2,4,6-tri-t-butylphenyl) pentaerythritol-di-phosphite Among these, more preferable compounds are the above [7],
[8],

The compounds [9], [10], [11] and [12] are most suitable, and the compounds [7] and [8] are most suitable.

The amounts of the above-mentioned essential components used in the present invention are as follows based on 100 parts by weight of the propylene resin. [Metal salt of rosin]: 0.03 to 2 parts by weight, preferably 0.05 to 1 part by weight, particularly preferably 0.1 to 0.6 part by weight [tertiary amine type light stabilizer]: 0. 01 to 1 part by weight, preferably 0.02 to 0.5 part by weight, particularly preferably 0.
03-0.3 parts by weight [aromatic phosphite and / or aromatic phosphonite antioxidant]: 0.01-0.5 part by weight, preferably 0.03-0.4 part by weight, especially Preferably 0.05
~ 0.3 parts by weight

If the amount of the metal salt of rosin is too small, the transparency is insufficient. On the other hand, if the amount is too large, not only the transparency deteriorates, but it is also uneconomical. Further, if the amount of the tertiary amine type light stabilizer is too small, the heat aging resistance is poor. On the other hand, if the amount is too large, discoloration and bleeding problems occur and it is uneconomical. Further, if the amount of the aromatic phosphite ester and / or the aromatic phosphonite-based antioxidant is too small, the stability effect during molding is poor, while if it is too large, discoloration and bleeding problems occur. It is also uneconomical.

In the present invention, in addition to the above-mentioned essential components, if desired, optional components can be added within a range that does not significantly impair the effects of the present invention. As an optional component, various additives commonly used for polyolefins,
For example, other antioxidants, heat stabilizers, UV absorbers, light stabilizers, nucleating agents, fillers, flame retardants, colorants, lubricants, neutralizing agents, metal deactivators (rust inhibitors), dispersions Agent, optical brightener,
There are conductive agents, antistatic agents, molecular weight modifiers (peroxides, etc.), resins and elastomers other than those used in the present invention.

The extruded product of the present invention comprises the above-mentioned essential components and optional optional components, and is mixed and melt-kneaded by using a suitable mixer or kneader which is usually used to obtain a resin composition. None, which is obtained by molding this in an extruder. Here, as the kneading machine, a Henschel mixer, a super mixer, a V blender, a tumbler mixer, a ribbon blender, a Banbury mixer, a kneader blender, a single-screw or twin-screw kneading extruder and the like are suitably used, and the resin composition is preferably pellets. The thing of the shape is obtained. At this time, it is also possible to employ a so-called masterbatch system in which a propylene resin is preliminarily blended with a desired amount or more of the above-mentioned additive components and the mixture is extruded while being diluted with the propylene resin. Further, as the extrusion molding machine, a sheet molding machine, a hollow molding machine, a film molding machine, a pipe molding machine and the like which are generally used for polyolefin are used. Of the extrusion-molded products, the sheet-formed product may be subjected to secondary thermoforming such as vacuum forming, pressure forming, vacuum pressure forming and the like.

[0016]

The present invention will be further described below with reference to specific examples. Example 1 MFR 2.5 g / 10 minutes, ethylene content 3.0% by weight
0.1 parts by weight of calcium stearate as a neutralizing agent and 100 parts by weight of the propylene-ethylene random copolymer of No. 3, and mixed for 3 minutes with a super mixer, and heated to 250 ° C. Was melt-kneaded with an extruder having a screw diameter of 50 mmφ to obtain a resin composition. This resin composition was applied to an extruder heated to 230 ° C. and having a screw diameter of 35 mmφ and extruded from a T-shaped die having a width of 35 cm, and two metal rolls (hard chrome plating processing was performed) in which hot water of 60 ° C. was internally circulated. It has been sandwiched between the two) and cooled and solidified to produce a sheet having a thickness of 0.7 mm. At this time, the contamination state of the metal roll surface was visually evaluated. In addition, regarding the obtained sheet, JIS-K
Haze was evaluated according to 7105, and hue (b value) was evaluated with a color machine manufactured by Nippon Denshoku Co., Ltd. Further, this sheet was put in a gear oven at 120 ° C. and the deterioration time was measured. Table 2 shows the results.

Examples 2 to 5 and Comparative Examples 1 to 7 Sheets were produced and evaluated in the same manner as in Example 1 except that the additives shown in Table 1 were used instead of the additives. Table 2 shows the results.

[0018]

[Table 1]

[0019]

[Table 2]

As can be seen from Tables 1 and 2, a comparative example in which a compound other than a metal salt of rosin was compounded as a nucleating agent in the conventional compounding combination of a phosphorus-based antioxidant and a phenol-based antioxidant. In Nos. 1 and 2, roll contamination occurs and transparency is inferior, while in Comparative Example 3 in which a metal salt of rosin is blended, hue is inferior. On the other hand, in the examples in which the metal salt of rosin, the tertiary amine type light stabilizer and the phosphorus-based antioxidant were used in combination, all the results were satisfactory. Even if a metal salt of rosin was added, in the case of Comparative Examples 5 and 4 in which only the tertiary amine type light stabilizer or only the phosphorus-based antioxidant was used in combination, roll contamination occurred, the hue was inferior and the heat resistance was low. It is not preferable because the aging property is poor, and even if a tertiary amine type light stabilizer and a phosphorus-based antioxidant are used in combination, no nucleating agent is added in Comparative Example 7 or rosin. In Comparative Example 6 in which a nucleating agent other than the metal salt was blended, the results were unfavorable in terms of transparency and roll contamination.

[0021]

EFFECTS OF THE INVENTION According to the present invention, remarkable effects are obtained such that equipment contamination during extrusion molding is suppressed, and a propylene resin extruded product having excellent transparency, hue and heat aging resistance is obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location // B29K 23:00

Claims (2)

[Claims] 1. A propylene resin 100 parts by weight, a metal salt of rosin 0.03 to 2 parts by weight, a tertiary amine type light stabilizer 0.1.
01 to 1 part by weight, and aromatic phosphite and /
Or an aromatic phosphonite antioxidant 0.01 to
A propylene resin extruded product characterized by comprising 0.5 parts by weight. 2. The propylene resin extruded product according to claim 1, wherein the propylene resin is a resin having a melt flow rate of 0.1 to 50 g / 10 min.