JPS59113059A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:A composition obtained by blending a thermoplastic resin with a specific fluorine-contained polymer, showing improved lubricating effect with a small amount of it, having improved molding properties, providing molded articles having good appearance. CONSTITUTION:100pts.wt. thermoplastic resin is blended with 0.001-1pt.wt., preferably 0.005-0.7pt.wt. fluorine-contained polymer having a -SO3M group (M is alkali metal). A single polymer of a fluorine-contained vinyl compound shown by the formula (l and m are 0-4; n is 0 or 1; p is 0-12; R<1> and R<2> are F, or H; X<1> is F, Cl, or CF3; X<2> is F or CF3; Y<1> is X<2>; Y<2> is F or 1-10C perfluoroalkyl; M is alkali metal) or a copolymer of the compound and a fluorinated alpha-olefin compound shown by the formula FR<3>=CR<4>R<5> (R<3> is H or F; R<4> and R<5> are F, Cl, H, or CF3), fluorodivinyl compound, etc. is used as the fluorine-contained polymer, and especially a polymer whose substituent groups are all F is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition with excellent moldability. More specifically, the present invention relates to a thermoplastic resin composition containing a fluorine-containing polymer having a -803M group (M represents an alkali metal).

Thermoplastic resins, including polyolefins, usually contain lubricants to improve moldability.

On the other hand, apart from preventing the product from blocking, bleed-out of the lubricant onto the product surface also contaminates the surface of the product and the objects that come in contact with the product, so bleed out as much as possible. A lubricant with a small amount of lubricant is desired, and since adding a large amount of a lubricant may cause bleed-out, a lubricant that is highly effective even when added in a small amount is desired. In particular, attempts have been made to improve the mechanical strength and optical properties of polyolefins by increasing or narrowing the molecular weight, and polyolefins with high or narrow molecular weights have better extrusion processability than ordinary polyolefins. However, the commonly used lubricants such as higher fatty acids, alkali metal salts or alkaline earth metal salts of higher fatty acids are inferior to the lubricants, and molding is forced at low speeds, and there is a desire to develop lubricants with excellent lubricating effects.

From this point of view, the present inventors investigated lubricants that exhibit excellent lubricating effects when mixed in small amounts, and as a result, they discovered a fluorine-containing polymer having a -3o3M group and arrived at the present invention.

That is, in the present invention, the fluorine-containing polymer (B) having a 13o3M group (where M represents an alkali metal) is added to 100 parts by weight of the thermoplastic resin (A) in an amount of o, o o i to 1.0 parts by weight. The object of the present invention is to provide a thermoplastic resin composition having excellent moldability, which is characterized in that the composition is blended with a thermoplastic resin.

A typical fluorine-containing polymer (B) having a -3o31vl group (where M represents an alkali metal) used in the present invention has the general formula (1) (% formula %) (1) (However, in the formula, 1 is represents 0 or an integer of 1 to 4, m represents 0 or an integer of 1 to 4, n represents O or 1, p represents O or an integer of 1 to 12, R1 and R2 each represent an F atom or represents an H atom, Xl represents an F atom, a Cl atom or a -cF3 group, and X2 represents an F atom.
atom or 10 F3 group, Yl represents an F atom or -cF5 group, Y2 represents an F atom or a perfluoroalkyl group having 1 to 10 carbon atoms, M represents an alkali metal) Fluorine-containing vinyl compounds
A homopolymer of I or the compound and the general formula C! FR3=
aR'R5 (where R3 represents an H atom or an F atom, and R4 and R5 represent an F atom, a Cβ atom, a H atom, or -O
F6 group), for example, fluorinated α-olefin compounds such as tetrafluoroethylene, trifluorochloroethylene, hexafluoropropylene, trifluoroethylene, and vinylidene fluoride, general formula CH2-CR6R7 (However, R6, R7
represents a H atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic nucleus), such as ethylene, propylene, 1-butene, imbutylene, 1-pentene, 1-
hexene, 1-heptene, 5-methyl-1-butene, 4
-Olefin compounds such as methyl-1-pentene, styrene, and α-methylstyrene, with the general formula 0F2=OFOR” (
provided that R8 represents a perfluoroalkyl group having 1 to 10 carbon atoms);
Or C! F=C! F-CF=OF2, CF2-
It is a copolymer with a fluorodivinyl compound such as CFO(CF2)1-4oCF-CF2, and is preferably a perfluoropolymer having an SO3M group in which all substituents are F atoms.

Thermoplastic resin (A) blended with the fluorine-containing polymer (E)
) is not particularly limited as long as it exhibits fluidity when heated, and specific examples include low density polyethylene (high pressure method, medium/low pressure method), medium density polyethylene, high density polyethylene, polypropylene (homo, random). copolymers, block copolymers), polyolefins such as polybutene and poly4-methyl-1-pentene, ethylene such as ethylene/vinyl acetate copolymers, ethylene/acrylic acid copolymers, ethylene/vinyl alcohol copolymers, etc. Examples include copolymers, polyvinyl chloride, vinyl chloride polymers such as vinyl chloride/vinylidene chloride copolymers, polyamides, polyesters, polycarbonates, polystyrene, and ABS'J.

The thermoplastic resin composition of the present invention comprises a thermoplastic resin (A)
: 0, fluorine-containing polymer (B) per 100 parts by weight
t] 01 to 1.0 parts by weight, preferably 0.005
The composition contains 0.7 to 0.7 parts by weight. If the blending amount of the fluorine-containing polymer ω) is less than 0.001 part by weight, the effect of improving molding processability or the surface condition of the molded product will be small, and if it exceeds 1.0 part by weight, some parts of the extruder screw may This is not preferable because it increases slippage, makes extrusion moldability unstable, and tends to cause bleed-out to the surface of the molded product.

Various known methods can be used to obtain the thermoplastic resin composition of the present invention. Specifically, for example, each ingredient may be mixed with a Ribo blender, ■-blender, tanpla blender,
Examples include a method of mixing with a Henschel mixer or the like and then granulating with an extruder, or a method of melt-kneading with a single-screw extruder, multi-screw extruder, Niegoo mixer, Banbury mixer, roll, etc., followed by granulation or pulverization.

The thermoplastic resin composition of the present invention includes a weathering stabilizer, a heat stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent,
Various compounding agents, such as slip agents, pigments, dyes, nucleating agents, inorganic or organic fillers, reinforcing materials, etc., which are usually added to thermoplastic resins, are blended within the range that does not impair the purpose of the present invention. Good too.

As mentioned above, the thermoplastic resin composition of the present invention has superior lubricity compared to conventional compositions, so it does not cause load on the extruder even under high shear stress or high shear rate. , it is possible to obtain a molded product with a moated appearance,
In addition, even at conventional molding speeds, the surface of the molded product becomes rough and molding is forced to occur at low speeds.Of course, this is not the case for polyolefins with narrow molecular weight distribution and/or low melt flow rate. It has the characteristics of being able to obtain molded products with good appearance even when molded at high speeds.

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples in any way unless they go beyond the gist of the invention.

Examples 1 to 4 Melt Flow Ray): 0.9 g/10 m1n, density 20.954 g/C1n3 high-density polyethylene (trade name HI-XXX 5000S, manufactured by Mitsui Petrochemical Industries, Ltd.) =
100 parts by weight, 0.3 parts by weight and 0.1 parts by weight of dilauryl thiodipropionate and 3,5-di-t-butyl-4-hydroxytoluene as heat stabilizers, respectively, and fluorine-containing polymer (B). (where n is O to 13) (Product name: Nafion)
on) 501 (manufactured by DuPont) were mixed in the proportions shown in Table 1 and melt-kneaded using an extruder to obtain Composition-1.

Next, using the composition-1, a nozzle with a nozzle diameter (D) i mmφ, L/D = 15 was attached to a 20 mmφ extruder, and a full flight type screw was used to set the resin temperature to 260'C and the screw rotation speed. Extrusion molding of monofilament was carried out by changing the extrusion rate (g/min).
The extrusion pressure (kVcvr2) was measured and the surface smoothness of the monofilament was observed.

The lubricant effect is the extrusion pressure P1 at an extrusion rate of 1Qg/min.
o(kglo)12) and extrusion N20g/min to t6
Evaluation was made based on the extrusion pressure P 20 (kg/an2) and the surface smoothness of the monofilament at these extrusion rates.

"10" The smaller the value of 20, the better the lubricant effect. Regarding the surface smoothness of the monofilament, those with smooth and glossy surfaces are indicated by ○, and those with rough surfaces are indicated by ×. The results are shown in Table 1.

Comparative Examples 1 to 2 Tests were conducted under the same conditions as in Example 1, except that in place of the fluorine-containing polymer (B) in Example 1, no lubricant was added or calcium 12-hydroxystearate was used. The results are shown in Table 1.

Comparative Example 4 As the fluorine-containing polymer, polytetrafluoroethylene (trade name: Teflon (I6 Gloss), manufactured by Mitsui Fluorochemical Co., Ltd.) or polytetrafluoroethylene-6-fluoropropylene copolymer (
The test was conducted under the same conditions as in Example 1, except that Teflon ■100 (trade name, manufactured by Mitsui Fluorochemical Co., Ltd.) was used. The results are shown in Table 1.

Examples 5 to 7 and Comparative Examples 5 to 6 Melt flow rate: 1.2 g/10 min polypropylene (trade name Mitsui Petrochemical Polypropylene, T-
300) 100 parts by weight of 0.0% each of Ilkanox 1010 (manufactured by Chibato Iggy) and 6,5-di-t-butyl-4-hydroxytoluene as heat stabilizers. I M m
and 0.1 part by weight, and the compounds shown in Table 2 were further blended, and extrusion molding was performed at 260°C in the same manner as in Example 1 to examine the lubricant effect. The results are shown in 2nd Example 8.
-10 and Comparative Examples 7-8 Bo, 7. ．． Irganox 1oio (manufactured by Ciba Geigy) and Sandstub p-EPQ (manufactured by Sandoz) were added to 100 parts by weight of Tsua (trade name, -boitsu, □■525, manufactured by Mitsui Toatsu Chemical Co., Ltd.) as a heat-resistant stabilizer. 0.1 part by weight was blended, and the compounds shown in Table 6 were further blended, and the same test as in Example 1 was conducted at a molding temperature of 200°C. 5th result
Shown in the table.

Claims (1)

[Claims] (1) Thermoplastic resin (A): -
A thermoplastic resin composition comprising 0.001 to 1.0 parts by weight of a fluorine-containing polymer (B) having a 3o5M group (M represents an alkali metal).