JPH08151496A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic resin composition excellent in adhesiveness by mixing a thermoplastic fluororesin containing a specified organic fluorine compound in at least a specified amount with a polyether/polyamide block copolymer. CONSTITUTION: At least one organic fluorine compound selected among tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, etc., is (co)polymerized to give a thermoplastic, fluororesin (A) comprising a (co)polymer, such as a polyvinyl fluoride, containing at least 50 wt.% of these constituent units. The resin A is melt compounded with a polyether/polyamide block copolymer (B) wherein the chain of a poly(oxyalkylene) having a number-average molecular weight of about 300 to 6,000 is connected to the chain of a polyamide comprising a polymer of, e.g. a 6C or higher aminocarboxylic acid or lactam at a weight ratio of the resin A to the copolymer B of (1:99) to (99:1) at about 100-300 deg.C to give a thermoplastic resin composition excellent in adherence to fluororesin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition. Its purpose is to reduce the weight of the thermoplastic fluororesin, which has excellent adhesiveness, antistatic property, flexibility, and weather resistance.
It is to provide a polyether / polyamide block copolymer (hereinafter abbreviated as PEBA) having excellent chemical resistance and heat resistance.

[0002]

2. Description of the Related Art Thermoplastic fluororesins are used as 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, it has a drawback that it is difficult to combine or modify with multiple materials.

In order to improve these, for example, an alloy with polymethylmethacrylate (PMMA) (Japanese Patent Publication No. 43-
12012, etc.), composite with polycarbonate (JP-A-57-8244, etc.), polyolefin (JP-B-3-22901, etc.), modified polyolefin having a functional group (JP-A-62-57448, JP-A-62-57448). Others), a composite with polyimide (Japanese Patent Laid-Open No. 2-308856, etc.) and the like have been proposed, but they are not always sufficient.

On the other hand, PEBA is excellent in low temperature impact resistance, antistatic property, light weight and the like, and is used for tubes, hoses, industrial parts, ski boots and various sports shoes. However, chemical resistance, heat resistance, etc. are not sufficient, and the application is limited at present.

In order to solve these problems, many composites with various polymers have been proposed. For example, polyamide (PA) (Japanese Patent Publication No. 5-2150, etc.), polyester (Japanese Patent Publication No. 5-37179, etc.), polycarbonate (Japanese Patent Publication No. 60-141757, etc.), polyoxymethylene (Japanese Patent Publication No. 59- 191752, etc.), polyphenylene ether (JP-A-60-186560, etc.), polyolefin (JP-A-57-147520, etc.), polystyrene (JP-A-60-170646, etc.), polyvinyl chloride ( Japanese Patent Publication No. 3-2903, etc.), ionomers (Japanese Patent Publication No. 1-56096, etc.), polyepoxides (Japanese Patent Publication No. 2-50955, etc.), and the like, but it has been proposed to form a composite with many polymers. It was not always satisfactory from the viewpoints of weather resistance, chemical resistance, antifouling property, and the like.

[0006] Moreover, conventionally known compositions of thermoplastic fluororesins are completely soluble (PMMA) or macrophase-separated (many), and both of them mixed are microdispersed without a compatibilizing agent, and their characteristics Almost no system was found that complemented each other.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a thermoplastic fluororesin, which has PEB properties such as adhesiveness, antistatic property and flexibility.
A is intended to improve weather resistance, chemical resistance, antifouling property, flame retardancy, etc., and is a semi-micro-dispersed thermoplastic resin composition which is neither completely dissolved nor causes macrophase separation. It is provided.

[0008]

The present invention provides tetrafluoroethylene (TFE), trifluoroethylene, chlorotrifluoroethylene (CTFE), vinylidene fluoride (VDF), vinyl fluoride (VF), hexafluoropropylene ( HFP), a thermoplastic fluororesin (A) containing at least 50% by weight of at least one structural unit selected from perfluoroalkyl vinyl ethers, and a polyether / polyamide block copolymer (B). The thermoplastic resin composition is blended in a weight ratio of 1/99 to 99/1.

In the present invention, "thermoplastic fluororesin (A)" means TFE, trifluoroethylene, CTF.
It is a thermoplastic fluororesin containing 50% by weight or more of at least one structural unit selected from E, VDF, VF, HFE, and perfluoroalkyl vinyl ethers. Therefore, it is not limited to a homopolymer consisting of one kind of monomer (excluding polytetrafluoroethylene), and other components may be contained 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 copolymer 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, CTF).
E, HFP, etc.), polyvinyl fluoride (PVF) and its copolymers, polychlorotrifluoroethylene (PCTF)
E) and its copolymers, TFE / HFP copolymers (FE
P), TFE / perfluoroalkylvinyl ether copolymer (PFA), ethylene / TFE copolymer (ETF
E), ethylene / CTFE copolymer (ECTFE), and the like, and mixtures of these with other polymers (excluding PEBA) (however, the thermoplastic fluororesin is 50% by weight or more).

In the present invention, the "polyether / polyamide block copolymer (B)" means a poly (oxyalkylene) chain (a) and an aminocarboxylic acid having 6 or more carbon atoms or a lactam or a diamine having 6 or more carbon atoms. And a polyamide chain (b) which is a polymer of a salt of dicarboxylic acid. The one in which (a) and (b) are alternately linked via the dicarboxylic acid (c) having 4 to 20 carbon atoms is
It is generally called polyetheresteramide (hereinafter abbreviated as PEEA).

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 include poly (oxyhexamethylene), a block or random copolymer of ethylene oxide and propylene oxide, a block or random copolymer of ethylene oxide and tetrahydrofuran, and examples of the terminal group include a hydroxyl group, a carboxyl group, and an amino group. To be done.

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

Examples of the "salt (b) of aminocarboxylic acid having 6 or more carbon atoms or lactam or diamine having 6 or more carbon atoms and dicarboxylic acid" include, for example, ω-aminocaproic acid, ω-aminoenanthic acid and ω-aminocapryl. Acid, ω
-Aminopelargonic acid, ω-aminocapric acid, 11-
Aminocarboxylic acids such as aminoundecanoic acid and 12-aminododecanoic acid; lactams such as caprolactam, enantolactam, capryllactam, laurolactam; hexamethylenediamine adipate, hexamethylenediamine-sebacate, hexamethylenediamine-isophthalate Acid salt, undecamethylenediamine-adipate,
Examples include salts such as 4,4′-diaminodicyclohexylmethane-dodecane diacid salt, and the like.

Among these, 11-aminoundecanoic acid, 12-aminododecanoic acid, caprolactam, laurolactam, hexamethylenediamine-adipate, hexamethylenediamine-sebacate and the like are preferably used, depending on the purpose. . In addition, these components (b) are 2
You may use together 1 or more types.

In the present invention, "dicarboxylic acid having 4 to 20 carbon atoms (c)" includes terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid. ,
Aromatic dicarboxylic acids such as sodium 3-sulfoisophthalate; cyclohexanedicarboxylic acids, dicyclohexyldicarboxylic acids, decalindicarboxylic acids, norbornenedicarboxylic acids, alicyclic dicarboxylic acids such as adamantanedicarboxylic acids; succinic acid, oxalic acid, adipic acid, sebacine Examples thereof include acids and aliphatic dicarboxylic acids such as dodecanedioic acid. Of these, adipic acid, sebacic acid, dodecanedioic acid and the like are preferably used.

PEBA (B) used in the present invention
In the case of PEEA, for example, JP-B-56-4541
Conventional methods known in the gazettes of Japanese Patent No. 9 and Japanese Patent Publication No. 1-46528 can be used, but the methods are not limited to these.

In the present invention, the compounding ratio of (A) and (B) is 1/99 to 99/1 by weight. The preferred ratio is determined depending on the purpose and use. For example, 99/1 to 50/50, particularly 95/5 to 60/40 is preferable for imparting adhesiveness and antistatic property to fluororesin, and weather resistance to PEBA, chemical resistance, gasoline resistance, gas barrier property 60/40 to 1/99, preferably 50/50 for imparting antifouling property
-10/90.

The resin composition of the present invention is preferably melt-kneaded, and the method of melt-kneading can be semi-microdispersed 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 260 ° C. depending on the composition. .

In addition, 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, A crystal nucleating agent, a crystal accelerating agent, a plasticizer, a lubricant, a lubricant, a release agent, a flame retardant, a flame retardant auxiliary agent, a reinforcing agent, a filler, an adhesion auxiliary agent, an adhesive agent, etc. may be optionally contained. .

[0021]

The composition of the present invention is used as a thermoplastic fluororesin or PEBA resin having various characteristics, such as injection molded products, extrusion molded products, blow molded products, rotational molded products, specifically industrial parts, films, The composition is useful as a material for sheets, tubes, hollow containers, fibers, nonwoven fabrics, and the like.

[0022]

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. Unless otherwise specified in the examples,
"Parts" means "parts by weight". Further, various test pieces and characteristics are prepared, measured and evaluated by the following methods. (1) Melt index (MFR) of fluororesin According to ISO1133, it was measured at 250 ° C. under a load of 5 kg. Unit g / 10 minutes. (2) Relative viscosity of PEBA 2% of 0.5% orthochlorophenol solution of polymer
It was calculated from the solution viscosity at 5 ° C. (3) Preparation of test piece A predetermined amount of each pellet of fluororesin / PEBA was put in a blender and mixed, and then a film having a thickness of about 1 mm was prepared using a uniaxial extruder set to a cylinder temperature of 160 to 240 ° C. This film was cut into 5 cm squares to obtain test pieces for measuring antistatic property.

Further, a microdumbbell of ASTM D1708 was punched out from this film to obtain a chemical resistance test piece. On the other hand, 80 × 10 × 4 mm test piece for impact strength measurement is molded by using an injection molding machine with a mold clamping force of 80 tons and mixing the pelletized resin with a blender in a predetermined ratio and extruding with a uniaxial extruder. did. (4) Antistatic property After rubbing the above film with a polyester cloth for 30 seconds,
The tobacco ash was placed on a table with a height of 10 mm for 10 seconds. Depending on how the ash of the film was attached, it was evaluated in four grades of ⊚ (not attached at all), ∘ (almost attached), Δ (attached a little), and X (attached a lot). (5) Chemical resistance Set the above micro dumbbell to a radius of curvature of 5 mm,
After immersion in 50% caustic soda solution (alkali resistance), formic acid (acid resistance), and gasoline (gasoline resistance) at room temperature for 1 month, the surface change of the sample was observed. ○ indicates no change, ×
Means significant swelling or cracking, and Δ means intermediate. (6) Impact strength The test piece was provided with an ISO 179 type A notch, and the Charpy strength was measured.

The polymers used in the present invention are as follows. PVDF-1: 100% PVDF, MFR = 20. PVDF-2: PVDF and MFR copolymerized with 5% HFP
= 8. PVDF-3: PVDF and MF copolymerized with 20% TFE
R = 10. PVDF-4: PVDF and MF copolymerized with 9% CTFE
R = 7.

PEEA-1: A product obtained by reacting PA6 carboxylated with adipic acid at both ends with polyoxyethylene glycol having a number average molecular weight of 2000 at a ratio of 1/1. Relative viscosity 1.8. PEEA-2: A product obtained by reacting PA6 above with polyoxytetramethylene glycol having a number average molecular weight of 2000 at a ratio of 1/1. Relative viscosity 1.9.

PEEA-3: A product obtained by reacting PA12 whose both ends are carboxylated with dodecanedioic acid and polyoxyethylene glycol having a number average molecular weight of 2000 in a ratio of 1/1. Relative viscosity 2.0. PEEA-4: PA12 as above, with a number average molecular weight of 1000
2/1 with polyoxytetramethylene glycol of. Relative viscosity 1.9.

The above-mentioned various polymers were blended in a predetermined amount at each ratio shown in Tables 1 and 2. It was found that the composition of the present invention did not undergo phase separation and was not completely compatible by microscopic observation, but was dispersed in a fairly fine manner. These characteristics including the comparative example are shown in the right column of the table. It can be seen that the composition of the present invention has excellent balanced properties.

The film of Comparative Example 1 did not adhere to the polypropylene film, whereas the film of Example 2 adhered well to the polypropylene film and did not peel off easily. Furthermore, in Example 1, instead of PVDF-2, FEP (Example 12), ECTFE (Example 1)
Also when 3) was used, excellent antistatic property was exhibited.

Abbreviations other than the polymers used in Table 1 are as follows. Antistatic: Antistatic Alkali: Alkali resistance Acid: Acid resistance Gasoline: Gasoline resistance NB: No breakage.

[0030]

[Table 1]

[0031]

As described above, the composition of the present invention improves the alkali resistance and antistatic property of the thermoplastic fluororesin without phase separation, and the composition of the polyether / polyamide block copolymer resin is improved. It has improved chemical resistance and adhesiveness with other materials, and has excellent performance as various molded products including injection and extrusion.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Kazuyoshi Ohashi, Kazuyoshi Ohashi, 1 Awata-cho, Nakado-ji, Shimogyo-ku, Kyoto-shi, Elf Attochem Japan Co., Ltd. Kyoto Technical Center (72) Yukio Shinkai Shimogyo-ku, Kyoto-shi, Kyoto Chudo-ji Awatacho 1 Elf Atchem Japan Co., Ltd. Kyoto Technical Center

Claims (5)

[Claims] 1. At least one structural unit selected from tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene, and perfluoroalkyl vinyl ethers. The thermoplastic fluororesin (A) and the polyether / polyamide block copolymer (B), which are contained in an amount of at least 1% by weight, are 1/99 in weight ratio.
A thermoplastic resin composition characterized by being blended in a ratio of ˜99 / 1. 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 polyether / polyamide block copolymer is a polyetheresteramide. 4. The thermoplastic resin composition according to claim 1, wherein the thermoplastic fluororesin is a tetrafluoroethylene / hexafluoropropylene copolymer. 5. The thermoplastic resin composition according to claim 1, wherein the thermoplastic fluororesin is an ethylene / chlorotrifluoroethylene copolymer.