JPH08208927A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic fluororesin composition improved in adhe siveness, antistatic properties and alkali resistance by mixing a thermoplastic fluororesin with a polyether/polyester block copolymer and melt-kneading the mixture. CONSTITUTION: This thermoplastic resin composition is obtained by mixing a thermoplastic fluororesin (A) containing 50wt.% or above structural units derived from at least one member selected from among tri- and tetrafluoro- ethylenes, trifluorochloroethylene, vinylidene fluoride, hexafluoropropylene and perfluoroalkyl vinyl ether with a polyether/polyester block copolymer (B) in an A/B ratio of 99/1 to 50/50 and melt-kneading the mixture. According to this process, components A and B are micro-dispersed to form a system free from their disadvantages without using any compatibilizer. Component B is composed of a polyoxyalkylene chain (desirably 2-4C alkylene chain having a number-average molecular weight of 500-4000) bonded to a polyester chain of butylene terephthalate or the like which is a copolymer of a 6C or higher oxycarboxylic acid with a 6C or higher dicarboxylic acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition. The object is to provide a lightweight thermoplastic fluororesin composition having excellent adhesiveness, antistatic property, flexibility and the like.

[0002]

2. Description of the Related Art Thermoplastic fluorinated resins are used in paints, electric / electronic parts, steel pipe linings, chemical plant parts, weatherproof antifouling films, etc. as resins having excellent weatherability and chemical resistance. However, since it has almost no adhesiveness, there is a drawback that it is difficult to combine or modify with other materials.

In order to improve these, for example, an alloy with polymethylmethacrylate (PMMA) (Japanese Patent Publication No. 43-
12012, etc.), composites with polycarbonate (Japanese Patent Laid-Open No. 57-8244, etc.), polyolefins (Japanese Patent Publication No. 3-22901, etc.), modified polyolefins having functional groups (Japanese Patent Laid-Open No. Sho. 62-57448, etc.), a composite with polyimide (JP-A-2-308856, etc.) and the like have been proposed, but they are not always sufficient.
Moreover, conventionally known compositions of thermoplastic fluororesins are of the dissolution type (PMMA) or macro phase separation type (many), and the mixed two are microdispersed without a compatibilizing agent, and the characteristics of both are complementary. Almost no such system was found.

Japanese Patent Application Laid-Open No. 4-28760 discloses a composition of a polyester block copolymer and a fluororesin. In the patent, a small amount of fluororesin is blended to make a polyester / polyester block copolymer. It is intended to modify a polymer, and its purpose and constituents are different from those of the present invention.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to improve the adhesiveness, antistatic property, flexibility and the like of a thermoplastic fluororesin, and provides a semi-micro dispersed thermoplastic fluororesin composition. It is a thing.

[0006]

Means for Solving the Problems The present invention is directed to tetrafluoroethylene (hereinafter abbreviated as TFE), ethylene trifluoride, ethylene trifluoride chloride (CTFE), vinylidene fluoride (VDF), vinyl fluoride ( VF), hexafluoropropylene (HFP), thermoplastic fluororesin (A) containing at least 50% by weight of at least one structural unit selected from perfluoroalkyl vinyl ethers, and polyether polyester A thermoplastic resin composition comprising the block copolymer (B) and a weight ratio of (A) / (B) = 99/1 to 50/50.

In the present invention, "thermoplastic fluororesin (A)" means TFE, ethylene trifluoride, CTFE,
50 or more constitutional units selected from VDF, VF, HFP, and perfluoroalkyl vinyl ethers.
It is a thermoplastic fluororesin containing at least wt%. Therefore, it is not limited to a homopolymer consisting of one kind of monomer (excluding polytetrafluoroethylene), and other components may be added within a range of 50% by weight or less as long as the characteristics as a thermoplastic fluororesin are not impaired. It may be a copolymerized polymer contained or a mixture of these polymers.

Specific examples of the thermoplastic fluororesin include polyvinylidene fluoride (hereinafter abbreviated as PVDF) and its copolymer (examples of copolymerization components: TFE, CTFE, HF).
P, etc.), polyvinyl fluoride (PVF) and its copolymer, polytrifluoroethylene chloride (PCTFE) and its copolymer, TFE / HFP copolymer (FEP), TFE
/ Perfluoroalkyl vinyl ether copolymer (PF
A), ethylene / TFE copolymer (ETFE), ethylene / CTFE copolymer (ECTFE), TFE / perfluorodimethyldioxole copolymer and the like, and these and other polymers (however, polyester. A mixture with a polyester block copolymer (excluding TPEE hereinafter)) (however, the thermoplastic fluororesin is 50% by weight or more)
Is exemplified.

In the present invention, the "polyether / polyester block copolymer (B)" means a poly (oxyalkylene) chain (a) and an oxycarboxylic acid having 6 or more carbon atoms or a dihydroxy compound having 2 or more carbon atoms. Polyester chain (b) which is a polymer with a dicarboxylic acid having 6 or more carbon atoms
And are connected.

In the present invention, examples of the "poly (oxyalkylene) chain (a)" include poly (oxyethylene), poly (oxy-1,2- and 1,3-propylene), poly (oxytetramethylene), Examples thereof include poly (oxyhexamethylene), a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. Particularly, the number of carbon atoms in the alkylene portion is 2 to 2.
4 is preferable.

The number average molecular weight of the polyoxyalkylene chain is preferably in the range of 300 to 6000, and 500 to
4000 is particularly preferred.

Examples of the "polymer (b) of an oxycarboxylic acid having 6 or more carbon atoms or a dihydroxy compound having 2 or more carbon atoms and a dicarboxylic acid having 6 or more carbon atoms" include, for example, p-oxybenzoic acid and p-hydroxyethoxy. Benzoic acid, oxynaphthoic acid, hydroxyethoxynaphthoic acid; ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexane dimethanol, terephthalic acid, isophthalic acid, diphenyl dicarboxylic acid , Diphenoxyethanedicarboxylic acid,
Examples thereof include polyesters derived from diphenyl ether dicarboxylic acid, diphenyl ketone dicarboxylic acid, diphenyl sulfone dicarboxylic acid, naphthalene dicarboxylic acid and the like. You may use 2 or more types of these components.

Among these, butylene terephthalate, butylene terephthalate / isophthalate copolymer, ethylene terephthalate, butylene naphthalate and the like are preferably used, depending on the purpose. In addition, these (b)
Two or more kinds of components may be used in combination.

TPEE (B) used in the present invention
The weight ratio of the component (a) to the component (b) depends on the purpose and application, but is generally a / b = 20/80 to 90 /.
10, preferably 30/70 to 80/20.

In the present invention, the mixing ratio of (A) and (B) is (A) / (B) = 99/1 to 50/50 by weight.
Is. The ratio is preferably 95/5 to 60/40, but the preferred ratio is determined depending on the purpose and application.

The composition of the present invention may be directly blended with each resin in a predetermined proportion by dry blending, but it is preferably melt-kneaded in advance, and the method of melt-kneading is a compatibilizing agent by a conventionally known method. It is possible to disperse semi-micro without. For example, Banbury mixer, rubber roll machine,
Using a uniaxial or biaxial extruder, etc., usually 100 ~
300 ° C, preferably 160-280 ° C depending on the composition
It is possible to obtain a resin composition by melt-kneading at the temperature of.

The resin composition of the present invention includes a conventionally known antioxidant, thermal decomposition inhibitor, ultraviolet absorber, hydrolysis resistance improver, colorant (dye, pigment), antistatic agent, conductive agent, crystal nucleus. Agents, crystallization promoters, plasticizers, lubricants, lubricants, release agents,
A flame retardant, a flame retardant auxiliary agent, a reinforcing agent, a filler, an adhesion auxiliary agent, an adhesive agent and the like can be optionally contained.

[0018]

The composition of the present invention is a thermoplastic fluororesin having various characteristics, which is an injection-molded product, an extrusion-molded product, a blow-molded product, a rotationally-molded product, specifically an industrial part,
It is a useful material as a material for films, sheets, tubes, pipes, fibers, non-woven fabrics and the like. .

[0019]

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) Fluorine-based resin melt index (MFR) Measured at 230 ° C. under a load of 2.16 kg according to ISO1133. Unit g / 10 minutes. (2) Viscosity number of TPEE 2% of 0.5% orthochlorophenol solution of polymer
It was calculated from the solution viscosity at 5 ° C. (3) Preparation of test piece After each pellet of fluororesin / TPEE was placed in a blender in a predetermined amount and mixed, a film having a thickness of about 1 mm was prepared using a uniaxial extruder set to a cylinder temperature of 160 to 280 ° C. . This film was cut into 5 cm squares to obtain test pieces for measuring antistatic property. A microdumbbell of ASTM 1708 was punched out from this film to obtain a chemical resistance test piece.

On the other hand, the resin mixed at a predetermined ratio in a blender and extruded by a uniaxial extruder to be pelletized is used in an injection molding machine having a mold clamping force of 80 tons to obtain 80 × 10 × 4.
mm test pieces for measuring impact strength were prepared. (4) Antistatic property The surface specific resistance value of the film sample was measured. (5) Chemical resistance The above microdumbbell was set with a radius of curvature of 5 mm, immersed in 50% caseiso-da solution (alkali resistance), formic acid (acid resistance) at room temperature for 1 month, and then the surface of the sample. The change was observed. (6) Impact strength The Izod impact strength was measured by making an ISO180 type A notch on the test piece.

The main polymers used in the present invention are as follows. PVDF-1: PVDF homopolymer, MFR = 12. PVDF-2: PVDF and MF copolymerized with 10% HFP
R = 55. PVDF-3: PVDF and MF copolymerized with 25% TFE
R = 5. TPEE-1: 1 part of butylene terephthalate and polyoxytetramethylene glycol having a number average molecular weight of 2000
/ 3 reacted. Viscosity number 1.7.

TPEE-2: Butylene terephthalate /
Isophthalate (75/25) and number average molecular weight 2000
What was reacted with polyoxytetramethylene glycol in 1: 1. Viscosity number 2.2.

Various polymers were blended in a predetermined amount at each ratio shown in Table 1. The composition of the present invention was not phase-separated, and it was found by microscopic observation that it was not completely compatible, but was dispersed in a fairly fine manner. The film made of PVDF-1 alone (Comparative Example 1) did not adhere to the polypropylene film at all, whereas the film of Example 1 adhered to the polypropylene film.

The characteristics of molded articles obtained from these compositions, including the comparative examples, are shown in the right column of the table. The compositions of the present invention have been found to have well-balanced and superior properties.

[0025]

[Table 1]

Even when FEP (Example 6) or ECTFE (Example 7) is used in place of PVDF-1 in the above Example 1, the surface resistivity is of the order of 10 to the 11th power.
Shows antistatic property, no change in film surface after immersion in alkali, and good alkali resistance.

[0027]

As described above, the composition of the present invention improves the alkali resistance and antistatic property of the thermoplastic fluororesin without phase separation, and further increases the adhesiveness with other materials, It has excellent performance as various molded products including injection and extrusion.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kazuyoshi Ohashi, Kazuyoshi Ohashi, No. 1 Awata-cho, Nakado-ji, Shimogyo-ku, Kyoto, Japan Elf Atchem Japan Co., Ltd. Kyoto Technical Center (72) Inventor, Mayer Jerome Kyoto, Kyoto Elf Atchem Japan Co., Ltd. Kyoto Technical Center, 1 Awata-cho, Chudo-ji, Shimogyo-ku, Yokohama

Claims (5)

[Claims] 1. Tetrafluoroethylene, trifluoroethylene,
At least one constitutional unit selected from ethylene trifluoride chloride, vinylidene fluoride, vinyl fluoride, propylene hexafluoride, and perfluoroalkyl vinyl ethers
A thermoplastic fluororesin (A) containing 0% by weight or more,
A thermoplastic resin composition comprising the polyether / polyester block copolymer (B) in a weight ratio of A / B = 99/1 to 50/50. 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic fluororesin is polyvinylidene fluoride. 3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic fluororesin is a tetrafluoroethylene / propylene hexafluoride copolymer. 4. The thermoplastic resin composition according to claim 1, wherein the thermoplastic fluororesin is an ethylene / trifluorochloroethylene copolymer. 5. The thermoplastic resin composition according to claim 1, wherein the polyether / polyester block copolymer is a polyoxytetramethylene / polybutylene terephthalate block copolymer.