JP2014129465A - Composition, molded body and fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of providing a molded body or a fiber having excellent water repellent properties while maintaining or improving strength.SOLUTION: A composition contains polyester (I) and a fluorine resin (II), and the polyester (I) is 99 to 70 mass% and the fluorine resin (II) is 1 to 30 mass% based on a total 100 mass% of the polyester (I) and the fluorine resin (II), and the fluorine resin (II) has 10 or more carbonyl groups per 10carbon atoms in a main chain terminal or a side chain.

Description

The present invention relates to a composition, a molded body, and a fiber.

Patent Document 1 describes a biaxially oriented polyester film containing a polyester and a fluororesin, wherein the content of the fluororesin is from 1% by weight to 50% by weight.

Patent Document 2 includes a blend obtained by mixing a methylol group-containing fluorine-containing polymer (A) and a liquid crystal polyester (B), and the methylol group-containing fluorine-containing polymer (A) is There is provided a thermoplastic resin composition which is at least one selected from the group consisting of perfluoro polymers having 2 × 10 ² to 1 × 10 ⁵ methylol groups at the molecular chain terminals with respect to 1 × 10 ⁶ carbon atoms. Have been described.

JP 2004-217719 A International Publication No. 95/29956 Pamphlet JP-A-4-359031 JP-A-6-116430

Polyester, especially polyethylene terephthalate (hereinafter abbreviated as PET), is excellent in mechanical properties, chemical stability, transparency, etc., is inexpensive, and is widely used as various sheets, films, containers, fibers and the like. In recent years, however, it has been desired to further improve the water repellency of clothes and films.

However, in the prior art, in order to impart water repellency to the surface of the polyester resin, it is necessary to perform a pre-treatment for providing irregularities.
For example, Patent Document 3 discloses a water- and oil-repellent repellency characterized in that a film having a roughened surface is formed, and a chemisorption monomolecular film containing fluorine is formed on the surface via a siloxane bond. A film is described. Further, Patent Document 4 discloses a chemical adsorption containing an inorganic hard film having minute irregularities formed on at least one surface of a plastic film and fluorine formed on the minute irregularities on the inorganic hard film via a siloxane bond. Although a water / oil repellent film characterized by comprising a monomolecular film is described, there is a problem that productivity is poor.

In view of the above-mentioned present situation, the present invention provides a composition capable of obtaining a molded article or fiber having excellent water repellency while maintaining or improving the strength of a polyester resin.

The present inventors diligently studied about a composition capable of obtaining a molded article having excellent strength, and focused on a composition containing polyester and a fluororesin. Surprisingly, it has been found that a composition in which the fluororesin is finely dispersed in the polyester can be obtained by blending the fluororesin having a specific functional group and the polyester at a specific ratio, and this composition. The present invention has been completed by discovering that the use of the product can drastically improve the water repellency of the polyester resin while maintaining or improving the strength of the resulting molded article or fiber.

That is, this invention is a composition containing polyester (I) and fluororesin (II), Comprising: Polyester (I) is 99-99 with respect to a total of 100 mass% of polyester (I) and fluororesin (II). is 70 wt%, a fluorine resin (II) 1 to 30 wt%, the fluorine resin (II) is characterized by having a main chain terminus or a carbonyl group or 10 per 10 ⁶ carbon on the side chain It is a composition.

In the composition of the present invention, the fluororesin (II) is preferably dispersed in the polyester (I).

In the composition of the present invention, the average dispersed particle size of the fluororesin (II) is preferably 2.0 μm or less.

The fluororesin (II) is composed of a tetrafluoroethylene / hexafluoropropylene copolymer, a chlorotrifluoroethylene / tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and an ethylene / tetrafluoroethylene / hexafluoropropylene copolymer. It is preferably at least one selected from the group consisting of

Carbonyl group is carbonate group, haloformyl group, formyl group, the following formula:
^{-R 4 -C (= O) -R} 5
(Wherein R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and R ⁵ is a monovalent organic group having 1 to 20 carbon atoms), the following formula:
-O-C (= O) -R ⁶
(Wherein R ⁶ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms containing an etheric oxygen atom), a carboxyl group, an alkoxycarbonyl group, carbamoyl It is preferably a part of at least one organic group selected from the group consisting of a group, an acid anhydride bond, and an isocyanate group.

The present invention is also a molded article obtained by molding the above composition.

The molded body of the present invention is preferably a film or a sheet.

The present invention is also a fiber obtained by fiberizing the above composition.

Since the composition of this invention consists of the said structure, the molded object or fiber which is excellent in water repellency can be obtained, hold | maintaining or improving the intensity | strength of a polyester resin.

2 is a transmission electron micrograph of a test piece obtained from the composition produced in Example 1. FIG. 2 is a transmission electron micrograph of a test piece obtained from the composition produced in Example 2. FIG. 2 is a transmission electron micrograph of a test piece obtained from the composition produced in Example 3. FIG. 2 is a transmission electron micrograph of a test piece obtained from the composition produced in Comparative Example 1.

The present invention is described in detail below.

The composition of this invention contains polyester (I) and fluororesin (II) which has a carbonyl group, and polyester (I) is 99-99 with respect to a total of 100 mass% of polyester (I) and fluororesin (II). 70 mass%, and fluororesin (II) is 1-30 mass%.
In the prior art, blending polyester and polyvinylidene fluoride exclusively has been considered. This is because it was difficult to finely disperse the fluorine resin other than polyvinylidene fluoride in the polyester.
The composition of the present invention uses a fluororesin having a carbonyl group, and further blends the fluororesin and polyester at a specific ratio, so that even if a fluororesin other than polyvinylidene fluoride is used, A composition in which a fluororesin is finely dispersed is obtained. Thereby, it is possible to obtain a molded article and a fiber having excellent strength and excellent water repellency without imparting unevenness to the surface.
The composition of the present invention can also be referred to as a fluororesin / polyester resin composite.

Polyester (I) is a polycondensate of diol and dicarboxylic acid, and what is generally called polyester can be used.

Polyester (I) preferably has a melting point of 150 ° C. or higher and 300 ° C. or lower. When the melting point exceeds 300 ° C., the fluororesin (II) is not sufficiently dispersed, and a molded article having excellent strength and water repellency may not be obtained. If it is lower than 150 ° C., the polyester (I) may be thermally decomposed during kneading.
The melting point of the polyester (I) is more preferably 170 ° C. or higher, and further preferably 200 ° C. or higher. Moreover, it is more preferable that it is 280 degrees C or less, and it is still more preferable that it is 270 degrees C or less.
The melting point of the polyester (I) is obtained as a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimetry (DSC) apparatus.

Polyester (I) includes polyethylene terephthalate [PET], polybutylene terephthalate [PBT], polytrimethylene terephthalate [PTT], polyethylene naphthalate [PEN], polybutylene naphthalate [PBN], parahydroxybenzoic acid / ethylene terephthalate Examples include copolymers, hydroxynaphthoic acid / parahydroxybenzoic acid copolymers, biphenol / parahydroxybenzoic acid / phthalic acid copolymers, and the like.
The polyester (I) is preferably at least one resin selected from the group consisting of PET, PBT, PTT, PEN, and PBN from the viewpoint of molding processability.

The fluororesin (II) has a carbonyl group at the main chain terminal or side chain. In the present invention, the carbonyl group may be part of a functional group having —C (═O) —.

As the functional group having a carbonyl group, for example,
Carbonate group [—O—C (═O) —OR ³ (wherein R ³ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms including an etheric oxygen atom) ],
A haloformyl group [—C (═O) X ¹ , X ¹ is a halogen atom],
Formyl group [—C (═O) H],
Formula: —R ⁴ —C (═O) —R ⁵ (wherein R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and R ⁵ is a monovalent group having 1 to 20 carbon atoms. An organic group of
Formula: —O—C (═O) —R ⁶ (wherein R ⁶ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms including an etheric oxygen atom) A group represented by
Carboxyl group [—C (═O) OH],
An alkoxycarbonyl group [—C (═O) OR ⁷ (wherein R ⁷ is a monovalent organic group having 1 to 20 carbon atoms)],
Carbamoyl group [—C (═O) NR ⁸ R ⁹ (wherein R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms) )],
Acid anhydride bond [—C (═O) —O—C (═O) —],
An isocyanate group [—N═C═O],
Etc. can be mentioned as preferred functional groups.

Specific examples of R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Specific examples of R ⁴ include a methylene group, —CF ₂ — group, —C ₆ H ₄ — group, and specific examples of R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include a butyl group. Specific examples of R ⁷ include methyl group, ethyl group, propyl group, isopropyl group, butyl group and the like. Specific examples of R ⁸ and R ⁹ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a phenyl group.

Among these functional groups having a carbonyl group, a group consisting of a carboxyl group, a haloformyl group, an alkoxycarbonyl group, and a carbonate group from the viewpoint of ease of introduction into the fluororesin (II) and reactivity with other materials. It is preferably at least one selected from the group consisting of —COOH, —OC (═O) OCH ₂ CH ₂ CH ₃ , —COF, and —OC (═O) OCH (CH ₃ ) _2. More preferably, it is at least one selected.

The fluororesin (II) has 10 or more carbonyl groups with respect to 1 × 10 ⁶ carbon atoms. Preferably, it is 100-1000, More preferably, it is 100-600, More preferably, it is 150-450.
When the number of carbonyl groups is in the above range, a molded article or fiber having better water repellency and strength can be obtained from the composition of the present invention.
The number of carbonyl groups is calculated from the functional group amount determined from the absorbance of the carbonyl group by an infrared spectrometer (IR spectrometer).

The fluororesin (II) is, for example, a polymer having polymerized units based on at least one fluorine-containing ethylenic monomer.
The fluororesin (B) is preferably a melt processable fluororesin. By using a melt-processable fluororesin, the composition of the present invention can obtain a molded article or fiber having higher strength and excellent water repellency.

Examples of the melt processable fluororesin include tetrafluoroethylene (TFE) / hexafluoropropylene (HFP) copolymer, TFE / HFP / perfluoro (alkyl vinyl ether) (PAVE) copolymer, and TFE / PAVE copolymer. Copolymer [PFA], ethylene (Et) / TFE copolymer, Et / TFE / HFP copolymer, polychlorotrifluoroethylene [PCTFE], chlorotrifluoroethylene (CTFE) / TFE copolymer, CTFE / TFE / PAVE copolymer, Et / CTFE copolymer, TFE / vinylidene fluoride (VdF) copolymer, VdF / HFP / TFE copolymer, VdF / HFP copolymer, polyvinylidene fluoride (PVdF), polyvinyl fluoride (PVF). In addition, low molecular weight polytetrafluoroethylene (PTFE) can be used as long as it is melt processable.
As said PAVE, what has a C1-C6 alkyl group is preferable, and perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether) etc. are mentioned. .

Above all, as the fluororesin (II), a molded product or fiber having more excellent water repellency and strength can be obtained. Therefore, TFE / HFP copolymer, Et / TFE copolymer, and CTFE / TFE copolymer are used. At least one copolymer selected from the group consisting of polymers is preferred.

In the TFE / HFP copolymer, the HFP unit is more than 2% by mass, preferably 20% by mass or less, and more preferably 10 to 15% by mass.

The TFE / HFP copolymer may further be obtained by polymerizing other monomers as long as it has the above-described composition. For example, the TFE / HFP copolymer may be a TFE / HFP / PAVE copolymer. One of the preferred forms.

The Et / TFE copolymer preferably has an Et unit: TFE unit molar ratio of 20:80 to 80:20. If the Et unit content is less than 20:80, the mechanical strength may be inferior. If the Et unit content exceeds 80:20, the water repellency may not be good. More preferably, the molar ratio of Et units: TFE units is 35:65 to 55:45. The Et / TFE copolymer is a copolymer including a polymerized unit based on TFE and a polymerized unit based on Et, and may have a polymerized unit based on another fluorine-containing monomer.

The Et / TFE copolymer is at least one selected from the group consisting of other fluorine-containing monomers and monomers containing no fluorine in addition to Et units and TFE units as a monomer component. It is also one of the preferable forms that it has a monomer unit based on a seed monomer. The other fluorine-containing monomer is not particularly limited as long as it can be added to both ethylene and TFE, but a fluorine-containing vinyl monomer having 3 to 10 carbon atoms is easy to use. For example, hexafluoroisobutylene, _{CH 2 = CFC 3 F 6 H} , HFP and the like. Among them, the following general formula:
CH ₂ = CH-Rf ⁴
A fluorine-containing vinyl monomer represented by the formula (wherein Rf ⁴ represents a perfluoroalkyl group having 4 to 8 carbon atoms) is also one preferred form. Moreover, as a monomer which does not contain fluorine at all, the following general formula:
CH ₂ = ^{CH-R 1}
(In the formula, R ¹ is not particularly limited in carbon number and may contain an aromatic ring, and may contain a carbonyl group, an ester group, an ether group, an amide group, a cyano group, a hydroxyl group, or an epoxy group. R ¹ may not be fluorine.
In addition, the Et / TFE copolymer is an Et / TFE / HFP copolymer, which is one of the preferred embodiments. Further, other fluorine-containing monomers (excluding HFP) or fluorine are used at all. You may have a monomer unit based on the monomer which does not contain. The monomer other than ethylene and TFE is preferably 10 mol% or less, and more preferably 5 mol% or less of the total monomer component of the copolymer composed of ethylene and TFE. Et unit: TFE unit: The molar ratio of monomer units based on other fluorine-containing monomers or monomers not containing fluorine at all is 31.5-54.7: 40.5-64.7: It is preferable that it is 0.5-15.

In the CTFE / TFE copolymer, the molar ratio of CTFE units to TFE units is preferably CTFE: TFE = 2: 98 to 98: 2, more preferably 5:95 to 90:10, More preferably, it is 20: 80-90: 10.

The CTFE / TFE copolymer is preferably a copolymer comprising CTFE, TFE, and a monomer copolymerizable with CTFE and TFE. Monomers copolymerizable with CTFE and TFE include ethylene, VdF, HFP, CH ₂ = CX ³ (CF ₂ ) _n X ² (wherein X ³ is H or F, X ² is H, F or Cl, n is an integer of from 1 to 10.) the monomer represented by, PAVE, _{and, CF 2 = CF-OCH 2} -Rf 3 ( wherein, Rf ³ is a perfluoroalkyl of 1 to 5 carbon atoms An alkyl perfluorovinyl ether derivative represented by the following formula :), among which at least one selected from the group consisting of ethylene, VdF, HFP and PAVE is preferable, and it is PAVE. More preferred. In other words, the CTFE / TFE copolymer is preferably a CTFE / TFE / PAVE copolymer.
Examples of PAVE include those described above.
The molar ratio of CTFE units, TFE units, and monomer units copolymerizable with CTFE and TFE is the total monomer units of CTFE units and TFE units: monomer units copolymerizable with CTFE and TFE = It is preferable that it is 90-99.9: 10-0.1.

The fluororesin (II) is at least one selected from the group consisting of a TFE / HFP copolymer, a CTFE / TFE / PAVE copolymer, and an Et / TFE / HFP copolymer, among others. In particular, it is particularly preferable because a molded product or fiber excellent in water repellency and strength can be obtained.

The content of each monomer unit of the copolymer described above can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

The fluororesin (II) preferably has a melt flow rate (MFR) of 0.1 to 100 g / 10 min measured at a temperature appropriate for the resin type and a load of 5000 g, and 5 to 40 g / 10 min. It is more preferable that it is 10 to 40 g / 10 min. When the MFR is in the above range, the strength and water repellency of the molded product or fiber produced from the composition of the present invention can be improved.
The MFR of the fluororesin (II) is measured using a melt indexer according to ASTM D2116.
The measurement temperature and load of MFR are appropriately determined depending on the type of fluororesin. For example, when the fluororesin (II) is a TFE / HFP copolymer, the measurement is performed at 372 ° C. under a load of 5000 g. In the case of CTFE / TFE copolymer (including CTFE / TFE / PAVE copolymer), measurement is performed at 297 ° C. under a load of 5000 g. In the case of an Et / TFE copolymer (including an Et / TFE / HFP copolymer), measurement is performed at 265 ° C. under a load of 5000 g.

Although the melting point of the fluororesin (II) is not particularly limited, since the fluororesin (II) is efficiently dispersed in the polyester (I), a molded article and fiber having better strength and water repellency can be obtained. For example, it is preferable that it is 150-350 degreeC, It is more preferable that it is 175-300 degreeC, It is still more preferable that it is 190-275 degreeC.
The melting point of the fluororesin (II) is determined as a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimetry (DSC) apparatus.

The fluororesin (II) may be one that has been treated with ammonia by a known method.

In the composition of the present invention, the polyester (I) is 99 to 70% by mass and the fluororesin (II) is 1 to 30% by mass with respect to 100% by mass in total of the polyester (I) and the fluororesin (II). It is. When the content of the polyester (I) and the fluororesin (II) is in the above range, a composition in which the fluororesin (II) is finely dispersed in the polyester (I) is obtained, and a molded article obtained from the composition And the strength and water repellency of the fibers can be improved.
When fluororesin (II) exceeds 30 mass%, dispersion | distribution of fluororesin (II) in polyester (I) will become inadequate.
When the fluororesin (II) is less than 1%, excellent water-repellent molded articles and fibers cannot be obtained.
In the composition of the present invention, the polyester (I) is 95 to 75% by mass and the fluororesin (II) is 5 to 25% by mass with respect to 100% by mass in total of the polyester (I) and the fluororesin (II). It is preferable that it is 90-80 mass%, and it is more preferable that fluororesin (II) is 10-20 mass%.
Within the above range, the fluororesin (II) is easily dispersed in the polyester (I), and further, the characteristics of the fluororesin (II) can be sufficiently exerted. Therefore, a molded article and fiber having superior strength and water repellency. Is obtained.

In the composition of the present invention, the fluororesin (II) is preferably dispersed in the polyester (I).
The average dispersed particle size of the fluororesin (II) is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.5 μm or less. When the average dispersed particle size is in the above range, the strength of the molded product obtained from the composition is more excellent.
The lower limit of the average dispersed particle size is not particularly limited, but may be 0.001 μm, for example.

In the composition of the present invention, the maximum dispersed particle size of the fluororesin (II) is preferably 4.0 μm or less. More preferably, it is 1.0 μm or less. When the maximum dispersed particle size is in the above range, the strength of the molded product obtained from the composition is more excellent.

The average dispersed particle size and the maximum dispersed particle size of the fluororesin (II) can be obtained by observing the composition of the present invention with a confocal laser microscope or from a press sheet prepared from the composition of the present invention. The ultrathin section can be observed with a transmission electron microscope (TEM), and the obtained image can be binarized with an optical analyzer.

The composition of the present invention comprises polyester (I) and fluororesin (II). Although it may contain other components as necessary, from the viewpoint of producing a molded article and fiber having excellent water repellency and strength, the composition of the present invention is composed of 100% by mass of the other components. It is preferable that it is 1 mass% or less with respect to this, and it is preferable that the composition of this invention is a composition which consists only of polyester (I) and fluororesin (II).
Although it does not specifically limit as said other component, Fibrous reinforcement materials, such as whisker, such as potassium titanate, glass fiber, asbestos fiber, carbon fiber, ceramic fiber, potassium titanate fiber, aramid fiber, and other high-strength fibers Inorganic fillers such as calcium carbonate, talc, mica, clay, carbon powder, graphite and glass beads; colorants; inorganic or organic fillers usually used such as flame retardants; stabilizers such as minerals and flakes; silicone oil Lubricants such as molybdenum disulfide; pigments; conductive agents such as carbon black; impact resistance improvers such as rubber; and other additives.

Production of the composition of the present invention is carried out under normal conditions using a mixer such as a compounding mill, a Banbury mixer, a pressure kneader, and an extruder that are usually used to mix a composition such as a molding composition. Can be performed. Since the average dispersed particle size of the fluororesin (II) can be reduced, the mixer is preferably an extruder, and more preferably a twin screw extruder.
The screw configuration of the twin screw extruder is preferably L / D = 30 or more, more preferably L / D = 40 or more, and particularly preferably L / D = 50 or more. L / D is the effective length of the screw (L) / screw diameter (D).
From the above, the composition of the present invention is obtained by mixing the polyester (I) and the fluororesin (II) with a twin screw extruder having a screw configuration having an L / D of 30 or more. Is preferred.

Examples of the method for producing the composition of the present invention include a method in which polyester (I) and fluororesin (II) are mixed in a molten state.
By sufficiently kneading polyester (I) and fluororesin (II), a composition having a desired dispersion state can be obtained. Since the dispersion state affects the strength, water repellency, moldability, and fiberization of the molded body, selection of a kneading method should be appropriately performed so that a desired dispersion state is obtained in the molded body obtained from the composition. It is.

As a method for producing the composition of the present invention, for example, polyester (I) and fluororesin (II) are introduced into a mixer at an appropriate ratio, and the other components are added as desired. The method of manufacturing by melt-kneading above melting | fusing point of fluororesin (II), etc. are mentioned.

The above-mentioned other components may be added in advance to polyester (I) and fluororesin (II) and mixed, or may be added when blending polyester (I) and fluororesin (II). .

A molded body obtained by molding the composition of the present invention is also one aspect of the present invention.

The molded product of the present invention is generally used for thermoplastic compositions such as injection molding, extrusion molding, compression molding, blow molding, calender molding, and cast molding, depending on the type, application, and shape of the target molded body. It can shape | mold by the shaping | molding method currently used. A molding method combining the above molding methods can also be employed. Further, the composition of the present invention and another polymer may be combined and molded.

Various conditions relating to the molding machine in the method for producing a molded body are not particularly limited, and can be performed, for example, as conventionally known.
The molding temperature is preferably a temperature equal to or higher than the melting point of the polyester (I). The molding temperature is preferably a temperature lower than the lower one of the decomposition temperature of the fluororesin (II) and the decomposition temperature of the polyester (I). As such a molding temperature, it is preferable that it is 250-300 degreeC, for example.

It does not specifically limit as a shape of the said molded object, For example, it can be set as various shapes, such as a sheet form; a film form; a rod form;
The molded article of the present invention is particularly suitable for a sheet-like or film-like molded article because of its excellent tensile strength. Sheet-like and film-like molded articles are suitable for applications such as electric wires, conductor covers, toilet articles, and water-related articles.

The molded product obtained by molding the composition of the present invention has excellent strength and water repellency, and has heat resistance, chemical resistance, solvent resistance, strength, rigidity, low chemical permeability, dimensional stability, difficulty. Excellent flammability, electrical properties and durability. Therefore, it can be used for various applications that require the above characteristics.
For example, in the electrical / electronics / semiconductor field, CMP retainer ring, etching ring, silicon wafer carrier, semiconductor / liquid crystal manufacturing equipment parts such as IC chip tray, insulation film, small button battery, cable connector, aluminum electrolytic capacitor body case; In the field, thrust washers, oil filters, automatic air conditioner control unit gears, throttle body gears, ABS parts, AT seal rings, MT shift fork pads, bearings, seals, clutch rings; Cables for transportation systems, conveyor belt chains, connectors for oilfield development machinery, pump parts for hydraulic drive systems (bearings, port plates, ball joints for pistons); Check machine cabin interior parts, fuel line protective material; and food and beverage manufacturing equipment parts, medical instrument parts (sterilizing instruments, gas liquid chromatography) it can be used, for example.
Moreover, it is preferable that the molded object of this invention is a film or a sheet | seat, and since it is excellent in intensity | strength, it is suitable as a solar cell backsheet. Moreover, since it is excellent in water repellency, it is suitable as a water-repellent film.

The fiber obtained by fiberizing the composition of the present invention is also one aspect of the present invention.

The fiber of the present invention can be fiberized by a fiberizing method generally used for thermoplastic compositions such as melt spinning and solution spinning, depending on the type, application, shape, etc. of the target fiber. . Moreover, the fiberization method which combined the said fiberization method is also employable.
Further, the composition of the present invention and other polymer may be combined to form a fiber.

As the fiberizing method, a spinning machine or the like is used. Various conditions are not particularly limited, and can be performed, for example, as conventionally known.
Usually, the temperature at which the fiber is formed is preferably equal to or higher than the melting point of the polyester (I) used. Moreover, it is preferable that the temperature at the time of fiberizing is a temperature lower than the lower one of the decomposition temperature of the fluororesin (II) and the decomposition temperature of the polyester (I). Such a fiberizing temperature is preferably, for example, 250 to 300 ° C.

The fiber obtained by fiberizing the composition of the present invention has excellent water repellency and strength, heat resistance, chemical resistance, solvent resistance, strength, rigidity, low chemical permeability, dimensional stability, flame retardancy Excellent in electrical properties, electrical properties and durability. Therefore, it can be used for various fibers that require the above characteristics.
For example, it can be used as a fiber for clothes.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

<Measurement of MFR>
According to ASTM D2116, using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the mass (g / 10 minutes) of the polymer flowing out from a nozzle having an inner diameter of 2 mm and a length of 8 mm per 10 minutes was determined.
In the fluororesin (1), measurement was performed at a temperature of 372 ° C. and a load of 5000 g.
In the fluororesin (2), the measurement was performed at a temperature of 297 ° C. and a load of 5000 g.
In the fluororesin (3), measurement was performed at a temperature of 265 ° C. and a load of 5000 g.

<Preparation of tensile strength and water contact angle measurement specimen>
A test piece used for measurement of tensile strength was prepared by punching a type V dumbbell described in ASTM D-638 from a sheet having a thickness of 0.1 mm obtained by extrusion molding. The contact angle to water was measured by making the composition of the present invention into a sheet having a thickness of 1 mm by heat pressing, and measuring the contact angle of the sheet.

<Calculation of average dispersed particle size / maximum dispersed particle size>
The pellets produced by the twin screw extruder are trimmed with a razor for trimming so that the tip is 1 mm square, and then fixed to a sample holder of an ultramicrotome (Leica ULTRACUT S), and the chamber is filled with liquid nitrogen − After cooling to 80 ° C., the test piece was trimmed. The obtained test piece was observed with a color 3D laser microscope (VK-9710 manufactured by KEYENCE, Inc.) to observe the trimmed internal structure of the test piece, and the average dispersed particle size of the dispersed phase was determined.

<Tensile strength>
The tensile strength was measured using AUTOGRAPH AGS-J (manufactured by Shimadzu Corporation). The measurement was performed according to ASTM-D638 and the elongation until the test piece broke and the tensile strength were determined.

<Contact angle with water>
The contact angle with water was measured by Drop Master 701 (manufactured by Kyowa Interface Science Co., Ltd.). The measurement was performed using 2 microliters of pure water droplets.

<Number of carbonyl groups>
The number of carbonyl groups is measured by the functional group amount determined from the absorbance of the carbonyl group by an infrared spectrometer (IR spectrometer).
Specifically, a fluororesin was sandwiched between press dies at room temperature, and pressurized to 4 MPa with a hydraulic press to create a 0.2 mm thick film.
The infrared absorption spectrum of the prepared film was analyzed to calculate the number of carboxylic acid terminals.
In the case of a carboxylic acid terminal, a peak derived from a carbonyl group appears at an absorption wavelength of 1815 cm ⁻¹ [ν (C═O)]. Compared to the infrared absorption spectrum of a known film, the difference spectrum shows the following formula ( The number was calculated according to 1).
l: Absorbance K: Correction coefficient = 45.9
t: Film thickness (mm)
The correction factors for the target end groups are as follows.

Further, in the case of the NPP terminal, a peak derived from a carbonyl group of a carbonate group [—OC (═O) O—] appears at an absorption wavelength of 1810 to 1815 cm ⁻¹ [ν (C═O)]. = O) The absorbance of the peak was measured, and the number N of carbonate groups per 10 ⁶ main chain carbon atoms of the fluororesin was calculated by the following formula (2).
N = 500 AW / εdf (2)
A: Absorbance of ν (C═O) peak derived from carbonate group [—OC (═O) O—] ε: Mole of ν (C═O) peak derived from carbonate group [—OC (═O) O—] The absorbance coefficient is ε = 170 (1 · cm ⁻¹ · mol ⁻¹ ).
W: Average molecular weight of the monomer calculated from the composition of the fluororesin d: Film density (g / cm ³ )
f: Film thickness (mm)

In the examples and comparative examples, the following materials were used.
Polyester (1): (Product name: Polyester resin (polyethylene terephthalate resin), manufactured by Unitika Ltd., melting point: 240 ° C.)
Fluorine resin (1): carboxylic acid-terminated tetrafluoroethylene / hexafluoroethylene copolymer, composition ratio TFE: HFP = 92: 8 (molar ratio), melting point: 260 ° C., MFR: 25.0 g / 10 min), carboxylic acid end number 353 per 10 ⁶ carbon atoms.
Fluororesin (2): NPP (n-propyl peroxide carbonate) -terminated chlorotrifluoroethylene / tetrafluoroethylene / perfluoro (propyl vinyl ether) copolymer, composition ratio CTFE: TFE: PPVE = 20: 77: 3 ( molar ratio), melting point: 245 ℃, MFR: 20.0g / 10 min) NPP terminal number 155 per 10 ⁶ carbon atoms.
Fluororesin (3): NPP-terminated ethylene / tetrafluoroethylene / hexafluoropropylene copolymer, composition ratio Et: TFE: HFP = 44: 46: 10 (molar ratio), melting point: 195 ° C., MFR: 20.6 g / 10 min) number NPP ends 155 per 10 ⁶ carbon atoms.
Fluororesin (4): stable terminal tetrafluoroethylene / hexafluoroethylene copolymer, composition ratio TFE: HFP = 92: 8 (molar ratio), melting point: 240 ° C., MFR: 25.0 g / 10 min) carboxylic acid number of terminal 2 per 10 ⁶ carbon atoms.

<Example 1>
Polyester (1) and fluororesin (1) at the ratio (parts by mass) shown in Table 1 were introduced from two feeders, and a cylinder temperature was measured using a twin screw extruder (φ15 mm, L / D = 62). The composition was manufactured by melt-kneading under conditions of 280 ° C. and a screw rotation speed of 300 rpm. Using the obtained composition, a test piece was prepared by the above-described method, and the tensile strength and the water contact angle (°) were measured. Moreover, the average dispersed particle diameter of the fluororesin was calculated using the sample produced by the above method. The fluororesin was dispersed in the polyester, and the average dispersed particle size of the fluororesin was 301 nm.

<Example 2>
Polyester (1) and fluororesin (2) at the ratio (parts by mass) shown in Table 1 were introduced from two feeders, and the cylinder temperature was measured using a twin screw extruder (φ15 mm, L / D = 62). The composition was manufactured by melt-kneading under conditions of 280 ° C. and a screw rotation speed of 300 rpm. Using the obtained composition, a test piece was prepared by the above-described method, and the tensile strength and the water contact angle (°) were measured. Moreover, the average dispersed particle diameter of the fluororesin was calculated using the sample produced by the above method. The fluororesin was dispersed in the polyester, and the average dispersed particle size of the fluororesin was 410 nm.

<Example 3>
Polyester (1) and fluororesin (3) in the proportions (parts by mass) shown in Table 1 were introduced from two feeders, and a cylinder temperature was measured using a twin screw extruder (φ15 mm, L / D = 62). The composition was manufactured by melt-kneading under conditions of 280 ° C. and a screw rotation speed of 300 rpm. Using the obtained composition, a test piece was prepared by the above-described method, and the tensile strength and the water contact angle (°) were measured. Moreover, the average dispersed particle diameter of the fluororesin was calculated using the sample produced by the above method. The fluororesin was dispersed in the polyester, and the average dispersed particle size of the fluororesin was 455 nm.

<Comparative Example 1>
Polyester (1) and fluororesin (4) at the ratio (parts by mass) shown in Table 1 were introduced from two feeders, and a cylinder temperature was measured using a twin screw extruder (φ15 mm, L / D = 62). The composition was manufactured by melt-kneading under conditions of 280 ° C. and a screw rotation speed of 300 rpm. Using the obtained composition, a test piece was prepared by the above-described method, and the tensile strength and the water contact angle (°) were measured. Moreover, the average dispersed particle diameter of the fluororesin was calculated using the sample produced by the above method. The average dispersed particle size of the fluororesin was 4206 nm.

<Comparative example 2>
Using only the polyester (1), a test piece was prepared by the method described above, and the tensile strength and the water contact angle (°) were measured.

The composition of the present invention can be suitably used as a molded body such as a film or a fiber material.

Claims (8)

A composition comprising polyester (I) and fluororesin (II),
The polyester (I) is 99 to 70% by mass and the fluororesin (II) is 1 to 30% by mass with respect to 100% by mass in total of the polyester (I) and the fluororesin (II).
The fluorine resin (II), the composition characterized in that it comprises a main chain terminus or a carbonyl group or 10 per 10 ⁶ carbon in the side chain. The composition according to claim 1, wherein the fluororesin (II) is dispersed in the polyester (I). The composition according to claim 2, wherein the average dispersed particle size of the fluororesin (II) is 2.0 µm or less. The fluororesin (II) is a tetrafluoroethylene / hexafluoropropylene copolymer, a chlorotrifluoroethylene / tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and an ethylene / tetrafluoroethylene / hexafluoropropylene copolymer. The composition according to claim 1, 2 or 3, which is at least one selected from the group consisting of: Carbonyl group is carbonate group, haloformyl group, formyl group, the following formula:
^{-R 4 -C (= O) -R} 5
(Wherein R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and R ⁵ is a monovalent organic group having 1 to 20 carbon atoms), the following formula:
-O-C (= O) -R ⁶
(Wherein R ⁶ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms containing an etheric oxygen atom), a carboxyl group, an alkoxycarbonyl group, carbamoyl The composition according to claim 1, 2, 3, or 4, which is a part of at least one organic group selected from the group consisting of a group, an acid anhydride bond, and an isocyanate group. A molded article obtained by molding the composition according to claim 1, 2, 3, 4 or 5. The molded article according to claim 6, which is a film or a sheet. A fiber obtained by fiberizing the composition according to claim 1, 2, 3, 4 or 5.