JP3795186B2 - Polypropylene resin composition - Google Patents

Description

【００３３】
【発明の効果】
本発明のポリプロピレン樹脂組成物は融点が低く、伸縮性、柔軟性に優れるなどの特徴を有する繊維を提供し、又、加工性についても繊維紡糸時の糸の膠着等の問題がなく、産業上極めて価値がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a propylene resin composition suitable for fiber spinning, and more particularly to a syndiotactic polypropylene resin composition excellent in fiber fiber sticking prevention property during spinning.
[0002]
[Prior art]
Syndiotactic polypropylene fiber has a lower melting point than conventionally used isotactic polypropylene, and has characteristics such as stretchability and flexibility, so it can be used as a crimpable fiber and heat-sealing fiber. Expected.
[0003]
Syndiotactic polypropylene has the excellent characteristics as described above, but on the other hand, the crystallization speed is significantly slower than that of isotactic polypropylene, resulting in inferior workability such as fiber bundle sticking during spinning. It was.
[0004]
[Problems to be solved by the invention]
Methods for improving the processing characteristics of syndiotactic polypropylene include the addition of nucleating agents and blending with isotactic polypropylene, but the effect is insufficient, and productivity is not achieved by methods such as changing spinning conditions. There has been a problem of a significant drop.
[0005]
Accordingly, an object of the present invention is to provide a polypropylene resin composition suitable for fiber spinning.
[0006]
Another object of the present invention is to provide a propylene resin composition which is free from sticking of yarn during fiber spinning and has excellent spinning workability.
[0007]
[Means for Solving the Problems]
The present inventors diligently studied on a method for solving the above-described problems, and completed the present invention.
[0008]
That is, the propylene resin composition for fiber spinning of the present invention comprises 70 to 90 parts by weight of syndiotactic polypropylene, 10 to 30 parts by weight of isotactic polypropylene, 0.3 to 1 part by weight of silicone oil, and diamine and monocarboxylic acid. Or a polycondensate of diamine, monocarboxylic acid and polybasic acid in an amount of 0.05 to 0.5 parts by weight.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The syndiotactic polypropylene used in the present invention is exemplified by a homopolymer of a syndiotactic polypropylene or a copolymer with a small amount of another olefin, and the tacticity is 13C in the case of a homopolymer. -The syndiotactic (racemic) pentad fraction measured by NMR is preferably 0.7 or more, more preferably 0.8 or more. In the case of a copolymer, absorption of the methyl group of propylene at the center of the racemic pentad The absorption observed at about 20.2 ppm is preferably 0.5 or more, particularly preferably 0.6 or more, based on the total absorption of methyl groups of propylene.
[0010]
Such syndiotactic polypropylene is produced, for example, by polymerization using a catalyst system comprising a metallocene catalyst such as diphenylmethylene (cyclopentadienyl-1-fluorenyl) zirconium dichloride and a methylaluminoxane cocatalyst, As the polymerization method, any of solvent polymerization method, bulk polymerization method, gas phase polymerization method and the like may be used.
[0011]
The isotactic polypropylene used in the present invention has a relatively high tacticity of 0.7 or more as an isotactic (meso) pentad fraction measured by 13C-NMR, and is an isotactic polypropylene alone. Polymers, propylene-ethylene random copolymers, etc. can be exemplified, but when considering the flexibility of the fiber and the performance as a heat-fusible fiber, the propylene-ethylene random copolymer is more preferable than the polypropylene homopolymer. Is preferably used.
[0012]
These isotactic polypropylenes can be used as usual commercial products as they are. However, in the case of production, for example, a catalyst system comprising a magnesium chloride-supported titanium catalyst, a triethylaluminum promoter and various external donors (electron-donating compounds) is used. As in the case of the syndiotactic polypropylene, any of a solvent polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used.
[0013]
In the case where a polypropylene-ethylene random copolymer is used as isotactic polypropylene, the ethylene content is preferably 1.0% by weight or more, more preferably 3.0 to 5.0% by weight. If the ethylene content is less than 1.0% by weight, the flexibility and heat-sealing characteristics of the fiber will be insufficient.
[0014]
With respect to the ratio of syndiotactic polypropylene and isotactic polypropylene shown here, a molded product having excellent moldability can be obtained within the range of 70 to 100 parts by weight of the former and 0 to 30 parts by weight of the latter. If the mixing ratio is out of this range, the flexibility and heat-sealing characteristics of the molded product are significantly hindered, which is inappropriate. More preferable mixing ratio is 70 to 90 parts by weight of syndiotactic polypropylene and 10 to 30 parts by weight of isotactic polypropylene.
[0015]
Silicone oils used in the present invention include dimethylpolysiloxane type, methylhydrogenpolysiloxane type, both-end hydrogenpolysiloxane type, methylphenylpolysiloxane type, alkyl-modified silicone type, amino-modified silicone type, carboxyl-modified silicone type. Higher fatty acid-modified silicone type, epoxy-modified silicone type, vinyl group-containing silicone type, alcohol-modified silicone type, polyether-modified silicone type, alkyl / polyether-modified silicone type, fluorine-modified silicone type, and the like. Although those generally available in the market can be used as they are, those having a viscosity measured at 25 ° C. of 100 to 4000 cSt are preferably used. Specific examples include TSF-451 (manufactured by Toshiba Silicone), SH200 (Toray Dow Corning Silicone), KF96 (Shin-Etsu Silicone), and the like.
[0016]
The amount of silicone oil added in the present invention is 0.1 to 5 parts by weight, preferably 0.3 to 1 part by weight, based on 100 parts by weight of the total of syndiotactic polypropylene and isotactic polypropylene. When this addition amount exceeds 5 parts by weight, the extrusion behavior during granulation and spinning deteriorates, making it difficult to obtain a stable product. On the other hand, when the amount is less than 0.1 parts by weight, the effect as an anti-sticking agent becomes insufficient.
[0017]
In addition, examples of the anti-sticking agent other than silicone oil include fatty acid ester-based, higher alcohol-based, amine-based, etc., as described in the comparative examples described later, when these are added, during spinning, Smoke is generated immediately after being pushed out of the die, and the working environment may be deteriorated.
[0018]
The polycondensate of diamine and monocarboxylic acid or the polycondensate of diamine, monocarboxylic acid and polybasic acid in the present invention is commercially available as a processing aid (wax) having a high softening point in the market. Can be used as is. Specific examples include Kao wax EB-P (manufactured by Kao) and light amide WH-215 (manufactured by Kyoeisha Chemical).
[0019]
As the diamine in the polycondensate of diamine and monocarboxylic acid or in the polycondensate of diamine, monocarboxylic acid and polybasic acid, a diamine having 1 to 10 carbon atoms is preferable. For example, ethylenediamine, 1, Examples include 3-diaminopropane, hexamethylene diamine, para-xylene diamine, and isophorone diamine. Moreover, about monocarboxylic acid, a C10 or more saturated aliphatic monocarboxylic acid and hydroxy monocarboxylic acid are preferable, for example, a stearic acid, behenic acid, a montanic acid, a palmitic acid etc. are mentioned. As for the polybasic acid, in particular, a carboxylic acid having a dibasic acid or more is preferably used. Specifically, an aliphatic dicarboxylic acid such as sebacic acid or adipic acid, an aromatic dicarboxylic acid such as terephthalic acid, or cyclohexyl succinic acid. Alicyclic dicarboxylic acid and the like.
[0020]
In the present invention, the polycondensate of diamine and monocarboxylic acid or the polycondensate of diamine, monocarboxylic acid and polybasic acid is used in a total amount of 100 parts by weight of syndiotactic polypropylene and isotactic polypropylene. And 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight. When this addition amount exceeds 1 part by weight, the heat-sealing property of the molded product is deteriorated, and when it is less than 0.01 part by weight, the anti-sticking property is halved.
[0021]
If necessary, additives such as an antioxidant and a neutralizing agent can be added to the resin composition in the present invention within a range in which it is usually used. In addition, a necessary amount of a rheology control agent such as an organic peroxide can be added to adjust the melt flow index (hereinafter abbreviated as MI) during granulation extrusion.
[0022]
The polypropylene resin composition of the present invention includes the above-mentioned syndiotactic polypropylene and isotactic polypropylene, silicone oil, polycondensate of diamine and monocarboxylic acid, or polycondensate of diamine, monocarboxylic acid and polybasic acid. If necessary, an antioxidant, a neutralizing agent, a nucleating agent, and other additives, for example, as a blended powder mixed with a Henschel mixer, or this blended powder, for example, a single-screw or twin-screw extruder, It can be obtained as pellets melt-granulated by a roll kneader.
[0023]
The melt viscosity is not particularly limited as long as it can be used as a raw material for forming fibers, but as a raw material used for ordinary melt spinning, MI measured at 230 ° C. is about 0.1 to 100 g / 10 minutes, It is generally 1 to 60 g / 10 min.
[0024]
The fiber using this resin composition can be used in any type, such as a single fiber spun only with this resin composition, or a composite fiber combined with another resin, such as a core-sheath type or a side-by-side type.
[0025]
The polypropylene resin composition obtained in this way is extremely superior in terms of heat-fusibility and flexibility compared to heat-fusible fibers that have been widely used in the market, and has been regarded as an initial problem. It is a resin composition excellent in production and practical use with improved sticking between yarns during fiber spinning.
[0026]
【Example】
Hereinafter, the present invention will be described in detail by way of examples.
[0027]
Each evaluation item was measured based on the following method.
(1) Fiber workability Using a 30 mmφ spinning machine, the resin is extruded from a die of 0.8 mmφ × 20 holes at a resin temperature of 210 ° C. and a gear pump speed of 5 rpm, and spinning at a cooling temperature of 90 ° C. and a roll speed of 10 m / min. When smoked, smoke generation, roll wrapping, etc. occurred.
(2) Adhesiveness Observed spun fiber bundles, those that are not agglomerated (fibers are broken) are ○, some are agglutinated, but those that are broken with fingers are △, overall Those that were stuck to the surface and could not be broken even with a finger were marked as x.
Reference example 1
[Production of syndiotactic polypropylene]
After replacing an autoclave having an internal volume of 200 liters with propylene, isopropylpentadienyl-1-fluorene synthesized according to a conventional method was lithiated therein, reacted with zirconium tetrachloride and recrystallized to obtain isopropyl ( Cyclopentadienyl-1-fluorenyl) zirconium dichloride (0.2 g) and Tosoh Akzo Co., Ltd. methylaluminoxane (degree of polymerization 16.1) (30 g) were charged. Next, 40 kg of liquid propylene was charged, the temperature was raised to 60 ° C., and polymerization was performed at the temperature for 1 hour. Next, 1 kg of methanol was charged and decalcified, and unreacted propylene was purged and filtered to obtain 20 kg of syndiotactic polypropylene.
[0028]
According to 13C-NMR, this polypropylene has a syndiotactic pentad fraction of 0.793, MI is 4.5 g / 10 min, and has a weight average molecular weight and number average molecular weight measured with 1,2,4 trichlorobenzene. The ratio (Mw / Mn) was 2.4.
[0029]
To 100 parts by weight of the syndiotactic polypropylene obtained above, 0.50 part by weight of silicone oil (TSF-451 manufactured by Toshiba Silicone Co., Ltd.) as an anti-sticking agent, and ethylenebisstearic acid amide (as a diamine / monocarboxylic acid polycondensate) Kao wax EB-P) 0.1 parts by weight, calcium stearate 0.02 parts by weight, Irgafos 168 (Ciba Geigy) 0.1 parts by weight, Irganox 1010 (Ciba Geigy) 0.05 Lupazole 101 (manufactured by Atochem Yoshitomi) was mixed with a Henschel mixer as an organic peroxide for adjustment of parts by weight and MI. Subsequently, the mixture was kneaded and granulated using a 50 mmφ extruder set at 230 ° C. to obtain pellets of MI 20 g / 10 min.
[0030]
Using the obtained pellets, the spinning processability and the sticking status of the fiber bundle were evaluated. As a result, smoke generation, roll wrapping, etc. did not occur, the fiber workability was good, and no sticking was found in the obtained fiber bundle. .
Example 2
100 parts by weight of polypropylene resin, 80% by weight of syndiotactic polypropylene and 20% by weight of isotactic polypropylene, a polypropylene-ethylene random copolymer having an ethylene content of 4.9% (Mitsui Toatsu Chemicals Mitsui Noblen MFL 4.9) %, And the same procedure as in Reference Example 1 was performed. Smoke and roll wrapping were not observed, the fiber processability was good, and no sticking was observed in the obtained fiber bundle.
Example 3
The same procedure as in Example 2 was performed except that the amount of silicone oil added as an anti-sticking agent was 0.3 parts by weight. Smoke and roll wrapping were not observed, the fiber processability was good, and no sticking was observed in the obtained fiber bundle.
Example 4
The same procedure as in Example 2 was conducted except that the amount of silicone oil added as an anti-sticking agent was 1.0 part by weight. As a result of the evaluation, no smoke generation or roll wrapping was observed, the fiber processability was good, and no sticking was observed in the obtained fiber bundle.
Comparative Example 1
The same procedure as in Reference Example 1 was conducted except that silicone oil was not added as an anti-sticking agent. As a result of evaluation, although no smoke was generated, the fiber bundle was stuck.
Comparative Example 2
Example 2 was repeated except that silicone oil was not added as an anti-sticking agent. As a result of evaluation, although no smoke was generated, the fiber bundle was stuck.
Comparative Example 3
The same procedure as in Example 2 was carried out except that the anti-sticking agent was Brian M-1 (manufactured by Matsumoto Yushi Seiyaku), which is a glycerin fatty acid ester, 0.5%. As a result of the evaluation, although the adhesiveness was good, smoke was generated near the die during spinning, and the spinning workability was poor.
Comparative Example 4
The same procedure as in Example 2 was conducted except that the anti-sticking agent was 0.5% of higher alcohol Calcoal 80 (manufactured by Kao). As a result of the evaluation, although the adhesiveness was good, smoke was generated near the die during spinning, and the spinning workability was poor.
Comparative Example 5
The same procedure as in Example 2 was conducted except that the anti-sticking agent was 0.5% of alkylamine armostat (manufactured by Lion). As a result of the evaluation, although the adhesiveness was good, smoke was generated near the die during spinning, and the spinning workability was poor.
[0031]
Table 1 summarizes the blending amounts and evaluation results of the raw materials of the above Examples and Comparative Examples.
[0032]
[Table 1]

[0033]
【The invention's effect】
The polypropylene resin composition of the present invention provides a fiber having characteristics such as a low melting point, excellent stretchability and flexibility, and there is no problem such as thread sticking during fiber spinning in terms of processability, Very valuable.

Claims (1)

Syndiotactic polypropylene 70 to 90 parts by weight, isotactic polypropylene 10 to 30 parts by weight, silicone oil 0.3 to 1 part by weight, and polycondensate of diamine and monocarboxylic acid or diamine and monocarboxylic acid and polybasic A polypropylene resin composition for fiber spinning comprising 0.05 to 0.5 parts by weight of a polycondensate with an acid.