JPH08302135A - Thermoplastic fluororesin composition and molded item produced therefrom - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic fluororesin compsn. which is excellent in softness, adhesive properties, antistatic properties, moldability, etc., and can provide a high-value-added molded item by compounding a thermoplastic fluororesin with a polyoxyalkylene. CONSTITUTION: 99.5-55wt.% thermoplastic fluororesin contg. at least 50wt.% structural vinylidene fluoride units is melt mixed and kneaded with 0.5-45wt.% polyoxyalkylene having a viscosity - average mol.wt. of 1,000-5,000,000. The resulting resin compsn. is injection molded, or is melt spun into fibers such as multifilaments, monofilaments, or staples, or is melt extruded into molded items such as films, sheets, plates, tubes, or pipes.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic fluororesin composition and a molded article thereof. The purpose is to provide a thermoplastic fluororesin composition that is excellent in moldability, flexibility, adhesiveness, antistatic property, etc., and that can be made into a molded product with higher added value by post-processing, and the molded product. To do.

[0002]

2. Description of the Related Art Thermoplastic fluorinated resins are used in paints, electric / electronic parts, steel pipe linings, chemical plant parts, weather resistant films, etc. as resins having excellent weather resistance and chemical resistance. However, since it has almost no adhesiveness, it has a drawback that it is difficult to combine or modify with other materials. Further, the fluororesin is less likely to be soiled than other resins, but has a drawback that it is difficult to remove when dust is generated by static electricity. In addition, since the fibers and films are difficult to draw from the viewpoint of viscosity and crystallinity, it is difficult to make fine and thin products, and in order to perform high speed molding, a product having a low degree of polymerization must be used, resulting in low strength. There was a flaw.

In order to improve these, for example, polymethylmethacrylate (PMMA) (JP-A-60-11091).
No. 2, etc.), an isobutylene copolymer (JP-A-54-1).
06622, etc.), acrylate (Japanese Patent Publication No. 56-2)
No. 0610, etc.) and blends of other fluororesins (Japanese Patent Publication No. 4-44012, JP-A-60-104514, etc.); plasticizers (JP-A-55-84413, etc.),
Polyolefin (JP-A-62-268811, etc.), metal soap (JP-A-61-174418, etc.), fluorocarbon wax (JP-A-60-115)
No. 652, etc.); or a combination thereof (Japanese Patent Laid-Open No. 6-101114, etc.), other special spinning, drawing method (Japanese Patent Publication No. 53-22574 and many others), etc. Not enough.

[0004]

DISCLOSURE OF THE INVENTION The present invention is intended to improve the moldability, flexibility, adhesiveness, antistatic property, etc. of a fluororesin, does not cause complete dissolution, and does not cause macrophase separation. The present invention provides a semi-micro dispersed thermoplastic fluororesin composition.

[0005]

According to the present invention, a thermoplastic fluororesin (A) containing at least 50% by weight of vinylidene fluoride as a constitutional unit of resin is 99.5 to 55% by weight.
And a polyoxyalkylene (B) in an amount of 0.5 to 45% by weight, and a thermoplastic fluororesin composition, and a molded article molded therefrom.

In the present invention, the "thermoplastic fluororesin (A)" is a thermoplastic fluororesin containing at least 50% by weight of vinylidene fluoride as a constitutional unit of the resin. Therefore, a homopolymer consisting of one type of monomer
The copolymer is not limited to the above, and may be a copolymer containing other components in a range of 50% by weight or less, or a mixture of these polymers, as long as the properties as the thermoplastic fluororesin are not impaired. Good.

Specific examples of the monomer component constituting the copolymerizable monomer component or the blendable polymer include tetrafluoroethylene (hereinafter abbreviated as TFE), trifluoroethylene, and trifluorochloroethylene. (CTFE),
Vinyl fluoride (VF), propylene hexafluoride (HF
P), ethylene (E), perfluoroalkyl vinyl ether and the like are exemplified.

The content of vinylidene fluoride in the thermoplastic fluororesin is at least 50% by weight, preferably 70% by weight or more, more preferably 90% by weight or more.

In the present invention, the "polyoxyalkylene (B)" is a combination of oxyalkylene units. Polyoxyalkylenes are generally obtained by condensation ring-opening polymerization of alkylene oxide with alkylene glycol for relatively low molecular weight products, and coordination ring-opening polymerization of alkylene oxides for high molecular weight products. Specific examples of polyoxyalkylene include poly (oxyethylene) and poly (oxy-
1,2- and 1,3-propylene), poly (oxytetramethylene), poly (oxyhexamethylene), block or random copolymer of ethylene oxide and propylene oxide, block or random copolymer of ethylene oxide and tetrahydrofuran And the like, and polyoxyethylene is particularly preferable from the viewpoint of post-processing.

The molecular weight of polyoxyalkylene is
Viscosity average 1000 to 5,000,000, preferably 10
000 to 1,000,000, particularly preferably 20000
600,000, but these are determined by the purpose and application. For example, when importance is attached to antistatic property and antifouling property, a product having a relatively low molecular weight (10,000 to 50,000) is used. When importance is attached to the sustainability of the performance, or when processability of molding is important, Those having a molecular weight (100,000 to 1,000,000) are preferable. An ultrahigh molecular weight product having a molecular weight of more than 5,000,000 is not preferable because the viscosity is too high and the thermal stability is rather high.

In the present invention, the mixing ratio of the thermoplastic fluororesin (A) and the polyoxyalkylene (B) is (A) / (B) = 99.5 / 0.5 to 55/45 by weight.
Is. The ratio is preferably 99/1 to 70/30, but the preferred ratio is determined depending on the purpose and use.

The composition of the present invention can be dry-blended with each resin in a predetermined ratio and directly molded, but it is preferable to melt-knead the resin (A) / (B) before molding, and melt-kneading. According to the method (1), semi-micro dispersion can be performed by a conventionally known method without a compatibilizer. For example, using a Banbury mixer, a rubber roll machine, a uniaxial or biaxial extruder, etc., a resin composition can be obtained by melt-kneading at a temperature of usually 100 to 300 ° C., preferably 150 to 270 ° C. although it depends on the composition. . In the subsequent injection molding or extrusion molding, the present composition has little increase in pressure due to viscosity even when high-speed molding is performed, and is excellent in moldability.

The composition of the present invention can be spun and stretched by a usual melt spinning method, and can be formed into a film by a usual melt extrusion method. The form of the fiber may be a multifilament, a monofilament, a staple, a woven fabric, a knitted fabric, a non-woven fabric, or the like, and the cross-sectional shape of the fiber may be any conventionally known one such as solid, hollow, and modified form. In particular, it is possible to use a non-woven fabric mixed with another material, which has been difficult in the past because of its excellent adhesiveness. The form of the film may be a film, a sheet, a plate, or the like. Furthermore, these molded products are water,
By extracting polyoxyalkylene with hot water, an organic solvent or the like, it is possible to process into ultrafine fibers, porous bulky flat material and the like. In particular, this composition is characterized in that it can be easily treated in an aqueous system.

The composition of the present invention contains a conventionally known antioxidant, thermal decomposition inhibitor, ultraviolet absorber, hydrolysis resistance improver,
Colorant (dye, pigment), antistatic agent, conductive agent, crystal nucleating agent, crystal accelerator, plasticizer, lubricant, lubricant, release agent, flame retardant, flame retardant aid, reinforcing agent, filler, Adhesion aids, pressure-sensitive adhesives and the like can be optionally contained.

[0015]

The composition of the present invention is a useful material as a material for fibers, films and the like as a thermoplastic fluororesin composition having various characteristics such as moldability, flexibility, antistatic property and adhesiveness.

[0016]

EXAMPLES The present invention will be specifically described below with reference to examples, but it goes without saying that the present invention is not limited to these examples. Incidentally, various test pieces and characteristics in the examples were prepared, measured and evaluated by the following methods. (1) Melt index (MFR) of fluororesin According to ISO1133, it was measured at 230 ° C. under a load of 2.16 kg. Unit g / 10 minutes. (2) Polyoxyalkylene (hereinafter abbreviated as POA)
The viscosity average molecular weight of the polymer was calculated from the solution viscosity of a 0.1% aqueous solution of the polymer at 35 ° C. using the empirical formula of Bailey et al. (3) Preparation of composition A predetermined amount of each pellet of fluororesin / POA was placed in a blender and mixed, and then a screw rotation speed was used using a uniaxial extruder having a 20 mmφ screw set to a cylinder temperature of 160 to 260 ° C. Extruded in a strand shape from a 3 mmφ die at 10 rpm, and pelletized the product,
The composition was for film formation and molding. (4) High-speed formability When the above-mentioned uniaxial extruder is used to form a strand, the screw
The judgment was made based on the head pressure when the number of revolutions was 10 rpm and the rate of increase in the head pressure when the number of revolutions was doubled from 10 rpm to 20 rpm. (5) Flexural modulus It was measured according to ISO178. (6) Impact strength Measured according to ISO180 / 1A. (7) Antistatic property A sheet having a thickness of 1 mm was prepared from the pellet prepared in (3), and the surface resistance was measured at 23 ° C and 50% relative humidity.

The polymers used in the present invention are as follows. PVDF-1: PVDF homopolymer, MFR = 20. PVDF-2: PVDF containing 15% by weight of HFP as a copolymerization component, MFR = 10. POA-2: Polyoxyethylene having a viscosity average molecular weight of 280,000 POA-3: Polyoxyethylene having a viscosity average molecular weight of 20,000 POA-4: Polyoxypropylene having a viscosity average molecular weight of 10,000

[0018]

Example 1 PVDF-1 / POA-1 in a weight ratio of 70
The mixture was blended at a ratio of / 30, extruded in a strand shape by a uniaxial extruder set at 250 ° C, and pelletized. The head pressure at the time of extrusion was 5 MPa, and even if the screw rotation speed was doubled, the pressure increase was only 1.4 times. The physical properties of the test piece prepared by using the pellet with an injection molding machine having a clamping force of 80 tons are as follows: flexural modulus 1100 MPa, impact strength 11 kg · cm / cm, surface resistivity 10 10 Ω. there were.

[0019]

Example 2 PVDF-1 / POA-in Example 1
In the same manner as in Example 1 except that the ratio of 1 was 95/5, the extrusion head pressure was 5 MPa, the pressure increase was 1.5 times, the bending elastic modulus was 1150 MPa, and the impact strength was 10 kg · cm / c.
m, and the surface specific resistance was 10 11 Ω.

[0020]

[Comparative Example 1] In the same manner as in Example 1, except that PVDF-1 alone was used for extrusion and molding, a head pressure of 8 MPa, a pressure increase of 1.8 times, a bending elastic modulus of 1800 MPa, and an impact strength of 5 were obtained.
The surface resistance was kg · cm / cm and the surface resistance was 10 14 Ω. Comparing with Examples 1 and 2, it can be seen that high-speed moldability, flexibility, antistatic property, etc. are remarkably improved by blending polyoxyalkylene.

[0021]

Examples 3 to 6 Instead of POA-1 in Example 1, POA-2 (Example 3), POA-3 (Example 4),
POA-4 (Example 5), PV instead of PVDF-1
DF-2 (Example 6, cylinder in this case-setting is 24
(0 ° C), the pressure increase when the screw rotation speed is doubled is 1.5 times, 1.4 times, 1.3 times and 1.3 times respectively, and the surface resistivity is Example 10 only 10
Of 11 and the other 10 was 10 10 Ω, and all showed excellent high-speed moldability and antistatic property.

[0022]

[Example 7] 0.3 mmφ using the pellet of Example 1
The filament was spun at 270 ° C. from a spinning machine having a spinneret with holes. When this fiber was observed under a microscope, it was found that it was not completely compatible but was dispersed in a fairly fine manner. Further, the adhesion of the present fiber to the polypropylene fiber was also good, and the fiber made of PVDF-1 alone (Comparative Example 1) did not adhere to the polypropylene fiber at all.

[0023]

As described above, the composition of the present invention has a small increase in pressure even at high speed molding, and the molded product has improved flexibility and antistatic property, and also has improved adhesiveness to other materials. And has excellent performance as a fiber, a film and the like.

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[Procedure amendment]

[Submission date] June 20, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

The polymers used in the present invention are as follows. PVDF-1: PVDF homopolymer, MFR = 20. PVDF-2: PVDF containing 15% by weight of HFP as a copolymerization component, MFR = 10. POA-1: Polyoxyethylene having a viscosity average molecular weight of 150,000
Emissions POA-2: viscosity average molecular weight 280,000 polyoxyethylene POA-3: viscosity average molecular weight of 20,000 polyoxyethylene POA-4: viscosity average molecular weight of 10,000 polyoxypropylene

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D01F 6/12 D01F 6/12 Z 6/48 6/48 C // (C08L 27/16 71: 02) B29K 27:12 B29L 23:00 (72) Kazuyoshi Ohashi, Kazuyoshi Ohashi, No. 1 Awata-cho, Nakadoji Temple, Shimogyo-ku, Kyoto City, Kyoto Elf Atchem Japan Co., Ltd. Kyoto Technical Center (72) Inventor, Mayer Jerome Elf Atchem Japan Co., Ltd. Kyoto Technical Center, 1 Awata-cho, Chudo-ji, Shimogyo-ku, Kyoto

Claims (5)

[Claims] 1. A thermoplastic fluororesin (A) containing 99.5 to 55% by weight of vinylidene fluoride as a constitutional unit of the resin, and a polyoxyalkylene (B) of 0.5 to 45% by weight. A thermoplastic fluororesin composition comprising: 2. The thermoplastic fluororesin composition according to claim 1, wherein the polyoxyalkylene is polyoxyethylene. 3. The thermoplastic fluororesin (A) and the polyoxyalkylene (B) are in a weight ratio of A / B = 99.
It is / 1-70 / 30, The thermoplastic fluororesin composition of Claim 1 characterized by the above-mentioned. 4. A thermoplastic fluororesin (A) containing 99.5 to 55% by weight of vinylidene fluoride as a constitutional unit of the resin, and a polyoxyalkylene (B) of 0.5 to 45% by weight. A molded article made of a thermoplastic fluorine-based resin composition, which comprises: 5. The thermoplastic fluororesin molded product according to claim 4, wherein the molded product according to claim 4 is one selected from an injection molded product, a fiber, a sheet, a film, a tube and a pipe. .