(19)
(11)EP 3 514 269 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
13.04.2022 Bulletin 2022/15

(21)Application number: 17850691.1

(22)Date of filing:  30.08.2017
(51)International Patent Classification (IPC): 
D01F 6/12(2006.01)
D01D 5/12(2006.01)
(52)Cooperative Patent Classification (CPC):
D01F 6/12; D01D 5/12
(86)International application number:
PCT/JP2017/031121
(87)International publication number:
WO 2018/051788 (22.03.2018 Gazette  2018/12)

(54)

VINYLIDENE FLUORIDE RESIN FIBERS AND SHEET-LIKE STRUCTURE

VINYLIDENFLUORIDHARZFASERN UND BLATTFÖRMIGE STRUKTUR

FIBRES DE RÉSINE À BASE DE FLUORURE DE VINYLIDÈNE, ET STRUCTURE SOUS FORME DE FEUILLE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 14.09.2016 JP 2016179948

(43)Date of publication of application:
24.07.2019 Bulletin 2019/30

(73)Proprietor: Kureha Corporation
Chuo-ku Tokyo 103-8552 (JP)

(72)Inventor:
  • SAIGUSA, Kotaku
    Tokyo 103-8552 (JP)

(74)Representative: Novagraaf Group 
Chemin de l'Echo 3
1213 Onex/ Geneva
1213 Onex/ Geneva (CH)


(56)References cited: : 
EP-A1- 3 570 336
JP-A- S6 028 510
JP-A- S57 143 511
JP-A- 2013 055 910
JP-A- 2018 074 001
US-A- 3 707 592
WO-A1-2016/147713
JP-A- S6 141 318
JP-A- S61 225 310
JP-A- 2018 074 000
JP-A- 2020 037 763
  
  • KEVIN MAGNIEZ ET AL: "Effect of drawing on the molecular orientation and polymorphism of melt-spun polyvinylidene fluoride fibers: Toward the development of piezoelectric force sensors", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 129, no. 5, 30 January 2013 (2013-01-30), pages 2699-2706, XP055065892, ISSN: 0021-8995, DOI: 10.1002/app.39001
  • YUKIKO NAMATAME: "Evaluation of crystalline polymer material using 2D-SAXS/WAX system (in Japanese)", RIGAKU JOURNAL (IN JAPANESE), vol. 49, no. 2, 31 December 2018 (2018-12-31), pages 14-14,
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Technical Field



[0001] The present invention relates to vinylidene fluoride resin fibers and a sheet-like structure.

Background Art



[0002] Due to vinylidene fluoride resins having excellent mechanical properties, their development is progressing to enable expanded applications into a variety of fields.

[0003] For example, Patent Document 1 discloses vinylidene fluoride resin molded product having a high Young's modulus and excellent surface characteristics and transparency.

[0004] Patent Document 2 discloses a vinylidene fluoride resin with improved tensile strength and a method for manufacturing the vinylidene fluoride resin.

[0005] Patent Document 2 also discloses that spinning vinylidene fluoride resin with a high draft ratio can provides a filament having a high birefringence, a large crystal size in the molecular chain direction, and excellent mechanical properties.

[0006] Patent Documents 3 to 5 and Document D6 disclose further vinylidene fluoride multifilament fibers and their production methods.

Citation List


Literature



[0007] 

Patent Document 1: JP S59-41310 A (published March 7, 1984)

Patent Document 2: JP S60-28510 A (published February 13, 1985)

Patent Document 3: US3707592 A (published December 26, 1972)

Patent Document 4: JPS6141318 A (published February 27, 1986)

Patent Document 5: JPS61225310 A (published October 7, 1986)

Document 6: Kevin Magniez et al.: "Effect of drawing on the molecule orientation and polymorphism of melt-spun polyvinylidene fluoride fibers: Toward the development of piezoelectric force sensors", Journal of applied polymer science, vol. 129, no. 5, 30 January 2013, pages 2699-2706.


Summary of Invention


Technical Problem



[0008] However, the filament obtained by the method of Patent Document 2 is manufactured by a unique spinning method that does not require a drawing process until it is wound as a filament from the spinneret. For this reason, melting conditions and cooling conditions need to be closely managed.

[0009] Furthermore, there is the problem that the range of management thereof is extremely narrow and the filament breakage often occurred. Additionally, as physical properties, the obtained filament demonstrates high mechanical strength but low elongation at break. For this reason, the expansion of applications of fibers constituted of such filaments is limited.

[0010] The present invention takes the above problems into consideration, and an object of the present invention is to provide a fiber that does not need close management in the manufacturing process and is can be applied in numerous applications.

Solution to Problem



[0011] The present inventors discovered that controlling the crystal structure of a fiber obtained using a plurality of vinylidene fluoride resin filaments provides a fiber that has excellent mechanical characteristics and does not result in the filaments breakage in the manufacturing process, and thereby achieved the present invention.

[0012] To solve the above problem, the vinylidene fluoride resin fiber according to the present invention, which is defined in the appended claims, is a fiber including a plurality of vinylidene fluoride resin filaments, wherein the fiber has a degree of crystal orientation of not less than 80% and a crystal size of not greater than 12 nm on the basis of X-ray diffraction from the azimuth angle intensity distribution curve of 2θ = 20.8 ± 1°.

[0013] The sheet-like structure according to the present invention is obtained using the vinylidene fluoride resin fiber of the present invention.

Advantageous Effects of Invention



[0014] The present invention can provide a fiber that does not need close management in the manufacturing process and can be applied in numerous applications.

Description of Embodiments



[0015] An embodiment of the vinylidene fluoride resin fiber according to the present invention will be specifically described below.

Vinylidene fluoride resin fiber



[0016] The vinylidene fluoride resin fiber according to the present embodiment (also simply called "fiber" hereinafter) is a fiber including a plurality of vinylidene fluoride resin filaments, wherein the fiber has a degree of crystal orientation of not less than 80% and a crystal size of not greater than 12 nm as determined on the basis of X-ray diffraction from the azimuth angle intensity distribution curve of 2θ = 20.8 ± 1°.

Filament



[0017] In the present embodiment, a filament signifies one single thread. The vinylidene fluoride resin filament according to the present embodiment (also simply called "filament" hereinafter) signifies a filament made from a vinylidene fluoride resin. Note that the vinylidene fluoride resin will be described in detail later.

[0018] The length of the filament according to the present embodiment may be determined as appropriate in accordance with the length of the fiber.

[0019] The diameter of the filament according to the present embodiment may be determined as appropriate according to the application of the fiber and the like. The diameter of the filament is preferably from 5 µm to 80 µm, more preferably from 10 µm to 60 µm, and even more preferably from 12 µm to 40 µm.

[0020] Note that in the present specification, the length of the filament indicates the size of the filament in the longitudinal direction. Furthermore, the diameter of the filament indicates the size of the filament in the direction perpendicular to the longitudinal direction.

Fiber



[0021] The fiber according to the present embodiment signifies a fiber structure including a plurality of vinylidene fluoride resin filaments. The fiber of the present embodiment is obtained by unifying a plurality of filaments, and generally signifies a format called multifilament.

[0022]  The number of filaments according to the present embodiment may be determined as appropriate according to the application of the fiber and the like, and is not particularly specified.

[0023] The length of the fiber according to the present embodiment may be determined as appropriate according to the application of the fiber and the like.

Degree of crystal orientation



[0024] In the present specification, the degree of crystal orientation signifies the degree of crystal orientation as determined on the basis of X-ray diffraction from the azimuth angle intensity distribution curve of 2θ = 20.8 ± 1°. The degree of crystal orientation is determined based on Equation (1) below.

[0025] [Equation 1]

(In the equation, β indicates the full-width at half maximum of the intensity peak in the azimuth angle intensity distribution curve.)

[0026] The degree of crystal orientation as determined on the basis of X-ray diffraction from the azimuth angle intensity distribution curve of 2θ = 20.8 ± 1° in the fiber according to the present embodiment is not less than 80%, preferably not less than 90%, and more preferably not less than 95%. The degree of crystal orientation is preferably in this range from the perspective that the mechanical strength of the filament and the fiber improves.

[0027] Note that in the present embodiment, the above degree of crystal orientation does not change depending on the number of filaments in the fiber according to the present embodiment.

Crystalline structure



[0028] The crystalline structure of the fiber according to the present embodiment is mainly β-phase, but may be an α-β mixture which includes α-phase in addition to β-phase, depending on the fiber manufacturing conditions to be described later. In a case where the crystalline structure is an α-β mixture, the ratio of α-phase to β-phase is not particularly limited. Note that the crystalline structure of the fiber according to the present embodiment does not include γ-phase.

Melting point



[0029] The fiber according to the present invention has two or more melting peaks in the range of 150°C to 180°C. The melting peak is measured by a differential scanning calorimeter (DSC). In the present embodiment, a melting peak of less than 170°C is defined as Tm1 and a melting peak of not lower than 170°C is defined as Tm2. Tm1 is preferably within the range of 150°C to 169.9°C, and preferably within the range of 160°C to 168°C. Tm2 is preferably within the range of 170°C to 180°C, and preferably in the range of 170.5°C to 178°C.

[0030] Note that the DSC melting peak is determined by increasing the temperature of the fiber at a rate of 10°C/minute in the temperature range of 25°C to 230°C.

[0031] In particular, the melting peak of Tml that appears within the range of 160°C to 168°C corresponds to the fact that the crystalline structure of the fiber undergoes a phase transition from the β-phase to the α-phase due to melting. Therefore, when Tm1 is in the range of 160°C to 168°C, the crystal orientation of the fiber proceeds through the drawing process to be described later, resulting in the crystalline structure of the fiber being β-phase. Thus, Tm1 within the range above is preferable from the perspective that the mechanical strength of the fiber increases. Note that the fiber according to the present embodiment is considered not to include γ-phase further based on the fact that a melting peak does not appear near 190°C.

Crystal size



[0032] In the present specification, crystal size is determined by the Scherrer equation shown in Equation (2) below.

[0033] [Equation 2]

(In the equation, D indicates the crystal size, k indicates a constant (0.9), λ indicates the wavelength of X-rays (Cu-Kα) (0.1542 nm (1.54 Å)), and β indicates the full-width at half maximum)

[0034] According to the present embodiment, use of a vinylidene fluoride resin fiber having the degree of crystal orientation and the crystal size described above can provide a fiber that has excellent mechanical characteristics and that does not result in the filament breakage in the manufacturing process.

Birefringence



[0035] In the present embodiment, the birefringence may be measured using a generally used compensator. Specifically, it is measured by the method described in the examples to be described later.

[0036] The birefringence of the fiber according to the present invention is not less than 30 × 10-3, preferably not less than 40 × 10-3, and more preferably not less than 45 × 10-3. The birefringence is preferably in this range from the perspective that the mechanical strength of the fiber improves.

Tensile strength



[0037] In the present embodiment, the tensile strength may be measured using a generally used tensile tester. Specifically, it is measured by the method described in the examples to be described later.

[0038] The tensile strength of the fiber according to the present embodiment is preferably not less than 2.0 cN/dtex, more preferably not less than 3.1 cN/dtex, and even more preferably not less than 3.5 cN/dtex.

Elongation at break



[0039] In the present embodiment, the elongation at break may be measured using a generally used tensile tester. Specifically, it is measured by the method described in the examples to be described later.

[0040] The elongation at break of the fiber according to the present embodiment is preferably not greater than 50%, more preferably not greater than 40%, and even more preferably not greater than 30%.

Vinylidene fluoride resin



[0041] In the present specification, vinylidene fluoride resin signifies a polymer containing a vinylidene fluoride (also called "VDF" hereinafter) monomer as the main component. The vinylidene fluoride resin in the present invention may be a vinylidene fluoride copolymer of a vinylidene fluoride monomer and another monomer, or may be a vinylidene fluoride homopolymer constituted of only one type of vinylidene fluoride monomer.

[0042] The other monomer according to the present embodiment is preferably at least one type selected from the group consisting of hexafluoropropylene, trifluoroethylene, tetrafluoroethylene, and chlorotrifluoroethylene.

[0043] The vinylidene fluoride copolymer according to the present embodiment contains preferably not less than 90 mol% and more preferably not less than 97 mol% of a vinylidene fluoride monomer, and is most preferably a vinylidene fluoride homopolymer. The content of vinylidene fluoride monomer is preferably in this range from the perspective that the mechanical strength of the fiber is enhanced.

Inherent viscosity



[0044] In the present embodiment, the inherent viscosity is determined by dissolving a sample in dimethylformamide as a solvent and measuring the time for which a certain volume of the liquid naturally drops in a capillary tube at 30°C by using an Ubbelohde viscometer.

[0045] In the present embodiment, the inherent viscosity of the vinylidene fluoride resin is preferably from 0.70 dL/g to 0.95 dL/g, and more preferably from 0.75 dL/g to 0.90 dL/g. The inherent viscosity is preferably in this range from the perspective of manifestation of spinnability and mechanical strength.

Method of manufacturing vinylidene fluoride resin fiber



[0046] An embodiment of the method of manufacturing the fiber according to the present embodiment (also called "the present manufacturing method" hereinafter) will be specifically described below, but the present manufacturing method is not limited to the method below.

[0047] The present manufacturing method is a method of producing a fiber by producing a plurality of filaments made from a vinylidene fluoride resin and unifying the filaments. The method includes an extrusion and discharge process, a spinning process, and a drawing process.

[0048] The vinylidene fluoride resin used in the present manufacturing method may be any vinylidene fluoride copolymers and vinylidene fluoride homopolymers. These vinylidene fluoride copolymers and vinylidene fluoride homopolymers may be manufactured by well-known polymerization methods and equipment. Furthermore, commercially available products may be used as the vinylidene fluoride copolymers and vinylidene fluoride homopolymers.

[0049] In the extrusion and discharge process, melted vinylidene fluoride resin is discharged in fiber form through the spinneret nozzle, and an un-drawn fiber of vinylidene fluoride resin is obtained. At that time, the vinylidene fluoride resin may be melted at, for example, from 240°C to 270°C. The hole diameter of the spinneret nozzle may be adjusted as appropriate depending on the inherent viscosity and the like of the vinylidene fluoride resin to be discharged, and may be, for example, from 0.10 to 1.00 mm.

[0050] From the perspective of assuring sufficient spinnability of the vinylidene fluoride resin, the vinylidene fluoride resin is preferably discharged while maintaining the temperature of the vinylidene fluoride resin at 70 to 155°C in the discharge process. Maintaining the temperature of the vinylidene fluoride resin in this manner may be performed for a certain time using, for example, a heating chamber directly below the spinneret nozzle.

[0051] Additionally, the un-drawn fiber of vinylidene fluoride resin is preferably solidified by cooling the discharged vinylidene fluoride resin. Such a process allows efficient drawing in the subsequent drawing process. Note that the method for cooling the vinylidene fluoride resin is not particularly limited, but air cooling is preferred from the perspective of convenience.

[0052] In the spinning process, the melted matter discharged in the discharge process is spun at a prescribed draft ratio. This can provide an un-drawn fiber of vinylidene fluoride resin having low orientation. The draft ratio in the spinning process is preferably low, for example, from 20 to 300.

[0053] Then, the obtained vinylidene fluoride resin filaments are unified into a single body by, for example, bundling the filaments with an oil ring or the like. Then, in the drawing process, the unified vinylidene fluoride resin filaments are drawn. Thus, the fiber according to the present embodiment is obtained.

[0054] In the drawing process, the drawing temperature of the unified vinylidene fluoride resin filaments is, for example, from 70 to 165°C, preferably from 80 to 160°C, and more preferably from 100 to 155°C. The draw ratio is, for example, from 2.50 to 6.00 times, preferably from 3.00 to 5.80 times, and more preferably from 3.40 to 5.60 times.

[0055] After the drawing process, a relaxation or heat treatment may be performed on the fiber. Thermal shrinkage of the fiber can be prevented by performing these treatments. Furthermore, these treatments increase the degree of crystallization of the fiber and cause the amorphous region to be rigid, and thereby enhance the strength of the fiber. The relaxation temperature in the relaxation treatment is, for example, from 100 to 180°C, preferably from 110 to 170°C, and more preferably from 120 to 165°C. The relaxation rate is, for example, from 0 to 20%, preferably from 0 to 17%, and more preferably from 0 to 15%. The temperature in heat treatment is, for example, from 100 to 180°C, preferably from 110 to 170°C, and more preferably from 120 to 165°C.

[0056] According to the present manufacturing method, the drawing temperature in the drawing process is from 80 to 155°C and the draw ratio is from 3.00 to 5.50. Drawing under such conditions promotes crystal orientation of the fiber, and causes the crystalline structure of the fiber to be β-phase. Therefore, the mechanical strength of the fiber can be further improved.

[0057] Due to the degree of crystal orientation of the fiber being not less than 80% and the crystal size being not greater than 12 nm as determined on the basis of X-ray diffraction from the azimuth angle intensity distribution curve of 2θ = 20.8 ± 1°, a fiber having tensile strength of not less than 2.0 cN/dtex and elongation at break of not greater than 50% can be obtained.

[0058] Additionally, a fiber having a birefringence of not less than 40 × 10-3, a tensile strength of not less than 3.1 cN/dtex, and an elongation at break of not greater than 40% can be obtained due to either of the two following conditions being satisfied:
  1. (i) the degree of crystal orientation of the fiber is not less than 90% as determined on the basis of X-ray diffraction from the azimuth angle intensity distribution curve of 2θ = 20.8 ± 1°, or (ii) one melting peak determined by DSC is present in each of two ranges, namely the range of 160°C to 168°C and the range of 170°C to 180°C.


[0059] Such a fiber is advantageously used for the sheet-like structure to be described later, for example.

Applications of vinylidene fluoride resin fiber



[0060] The vinylidene fluoride resin fiber according to the present embodiment may undergo treatments such as antistatic, flame-retardancy, flame-proofing, anti-bacterial, deodorization, and odor-resistance treatments or various surface processing treatments as necessary.

[0061] Furthermore, the sheet-like structure made from fiber according to the present embodiment may be produced by carrying out a process such as weaving or knitting using the vinylidene fluoride resin fiber according to the present embodiment. In this case, the process such as weaving or knitting may be carried out using well-known methods and equipment.

[0062] The sheet-like structure according to the present embodiment may also be a laminate including a plurality of sheet-like structures.

[0063] The sheet-like structure according to the present embodiment may be formed in a mesh form. In the sheet-like structure according to the present embodiment, the entire sheet may be formed in a mesh form or a portion of the sheet may be formed in a mesh form.

[0064] The format of the sheet-like structure according to the present embodiment is not particularly limited. For example, it may be used in various formats such as woven fabrics, knits, strings, cut fibers, papers, and nonwoven fabrics. The applications of the sheet-like structure are also not particularly limited. For example, it may be advantageously used in various industrial materials such as reinforced fibers for hollow fiber membranes, ropes and clothes, in base materials for medical use, in colored fibers, and in sensor devices as a piezoelectric substance. In a case where the sheet-like structure according to the present embodiment is formed in a mesh form, it may be advantageously used as, for example, a fishing net.

Summary



[0065] As described above, one aspect of the vinylidene fluoride resin fiber according to the present invention is a fiber including a plurality of vinylidene fluoride resin filaments, wherein the fiber has a degree of crystal orientation of not less than 80% and a crystal size of not greater than 12 nm as determined on the basis of X-ray diffraction from the azimuth angle intensity distribution curve of 2θ = 20.8 ± 1°.

[0066] Furthermore, the vinylidene fluoride resin has two or more melting peaks in the range of 150°C to 180°C.

[0067] In one aspect of the vinylidene fluoride resin fiber according to the present invention, the diameter of the filament is preferably not less than 5 µm and less than 80 µm.

[0068] According to the present invention, the birefringence is not less than 30 × 10-3.

[0069] In one aspect of the vinylidene fluoride resin fiber according to the present invention, the vinylidene fluoride resin is preferably a homopolymer of a vinylidene fluoride monomer.

[0070] In one aspect of the vinylidene fluoride resin fiber according to the present invention, the vinylidene fluoride resin may be a vinylidene fluoride copolymer of a vinylidene fluoride monomer and another monomer, and the other monomer is at least one type selected from the group consisting of hexafluoropropylene, trifluoroethylene, tetrafluoroethylene, and chlorotrifluoroethylene.

[0071] In one aspect of the vinylidene fluoride resin fiber according to the present invention, the vinylidene fluoride copolymer preferably contains not less than 90 mol% of a vinylidene fluoride monomer.

[0072] In one aspect of the vinylidene fluoride resin fiber according to the present invention, the inherent viscosity of the vinylidene fluoride resin is preferably from 0.70 dL/g to 0.95 dL/g.

[0073] In one aspect of the vinylidene fluoride resin fiber according to the present invention, preferably, the tensile strength is not less than 2.0 cN/dtex and the elongation at break is not greater than 50%.

[0074] In one aspect of the vinylidene fluoride resin fiber according to the present invention, more preferably, the birefringence is not less than 40 × 10-3, the tensile strength is not less than 3.1 cN/dtex, and the elongation at break is not greater than 40%.

[0075] One aspect of the sheet-like structure according to the present invention includes the vinylidene fluoride resin fiber of the present invention.

[0076] In one aspect of the sheet-like structure according to the present invention, the structure may be formed in a mesh form.

[0077] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope indicated in the claims. Embodiments obtained by appropriately combining the technical means disclosed by other embodiments are also included in the technical scope of the present invention.

Examples



[0078] The vinylidene fluoride resin fibers in the following examples and comparative examples were all manufactured using a spinning apparatus (available from Fiber Extrusion Technology Ltd.).

Example 1



[0079] The vinylidene fluoride resin used was pellet-formed polyvinylidene fluoride (called "PVDF" hereinafter; KF polymer available from Kureha Corporation; melting point 173°C; inherent viscosity 0.85 dL/g).

[0080] From the hopper of the spinning apparatus, the PVDF pellets were charged into a single screw extruder (cylinder diameter φ 25 mm), and the PVDF pellets were melted by heating at 265 to 270°C. The melted PVDF was spun at a draft ratio of 120 from a 24-hole nozzle (hole diameter 0.40 mm) using a gear pump, to produce 24 filaments made from PVDF, which were then coated with an oiling agent to produce a fiber made from PVDF. Then at in-line drawing process, the fiber was drawn at a drawing temperature of 80°C with a draw ratio of 4.50, and then the PVDF was heat treatment at a relaxation temperature of 130°C at a relaxation rate of 0% to produce a drawn fiber made from PVDF.

Example 2



[0081] A fiber was obtained in the same method as Example 1 except that the drawing temperature was 130°C and the draw ratio was 4.25.

Example 3



[0082] A fiber was obtained in the same method as Example 1 except that the drawing temperature was 130°C and the draw ratio was 3.50.

Reference Example 4



[0083] A fiber was obtained in the same method as Example 1 except that the drawing temperature was 130°C and the draw ratio was 3.00.

Example 5



[0084] A fiber was obtained in the same method as Example 1 except that the draft ratio was 60, the drawing temperature was 100°C, the draw ratio was 5.50, and the relaxation temperature was 100°C.

Example 6



[0085] A fiber was obtained in the same method as Example 1 except that the drawing temperature was 130°C, the draw ratio was 4.25, the relaxation temperature was 150°C, and the relaxation rate was 10%.

Comparative Example 1



[0086] A fiber was obtained in the same method as Example 1 except that the inherent viscosity of the PVDF used in Example 1 was changed to 1.00 dL/g, the diameter of the nozzle in Example 1 was changed to 2 mm, and the draft ratio was changed to 2550

Comparative Example 2



[0087] A fiber was obtained by subjecting the fiber obtained in Comparative Example 1 to a non-in-line drawing process. Specifically, after the un-drawn fiber obtained in Comparative Example 1 was temporarily wound, the wound un-drawn fiber was drawn to 1.16 times at a drawing temperature of 144°C in off-line drawing process.

Comparative Example 3



[0088] A fiber was obtained in the same method as Comparative Example 1 except that the draft ratio was changed to 10000.

Comparative Example 4



[0089] A fiber was obtained in the same method as Example 1 except that the inherent viscosity of the PVDF was changed to 0.68 dL/g and filaments made from PVDF were obtained with a nozzle diameter of 1 mm and a draft ratio of 850, and the fiber was not drawn in the subsequent process.

[0090] The manufacturing conditions in the above Examples 1 to 6 and Comparative Examples 1 to 4 are summarized in Table 1 below.

Evaluation of vinylidene fluoride resin fiber



[0091] The vinylidene fluoride resin fibers obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were evaluated with regard to filament diameter, average birefringence, degree of crystal orientation, crystal size, melting point (Tm1 and Tm2), tensile strength, and elongation at break. The results are shown in Table 1. The specific evaluation methods are described below.

Filament diameter



[0092] A filament of fiber of PVDF measuring 1 m long was measured at 20 points with a micrometer, and the average value was determined.

Average Birefringence



[0093] A fiber was sheared on the diagonal using a utility knife, and several drops of an immersion fluid (immersion oil: n = 1.516 (23°C)) were added dropwise onto the sheared surface of the fiber. The average birefringence (Δn) was determined by measuring retardation using a polarizing microscope and a Berek compensator available from Olympus Corporation.

Degree of crystal orientation



[0094] X-rays were irradiated onto a sample using an X-ray generator (available from Rigaku Corporation), and the intensity profile was measured using an imaging plate (IP). The light source was irradiated for 30 minutes at tube
voltage 40 kV and tube current 20 mA using Cu-Kα rays (0.1542 nm). The intensity profile for the azimuth angle direction of 2θ = 20.8 ± 1° was measured, and the degree of crystal orientation was calculated from the full-width at half maximum β using the following equation.


Crystal size



[0095] The intensity profile was fitted using peak separation software, and the crystal size was calculated using the Scherrer equation shown below.

(In the equation, D indicates the crystal size, k indicates a constant (0.9), λ indicates the wavelength of X-rays (Cu-Kα) (0.1542 nm (1.54 Å)), and β indicates the full-width at half maximum of the intensity peak in the azimuth angle intensity distribution curve.)

Melting point (Tm)



[0096] 5 mg of filaments were charged in an aluminum pan and the aluminum pan was sealed. The temperature was increased at a temperature increasing rate of 10°C/minute by using a differential scanning calorimeter (DSC-1 available from METTLER TOLEDO). The peak temperature of a peak appearing at lower than 170°C was defined as Tm1, and that appearing at not lower than 170°C was defined as Tm2.

Tensile strength and elongation at break



[0097] Using a Tensilon tensile tester (available from Orientec Co., Ltd.), tensile strength and elongation at break were measured five times with a test sample length of 300 mm and a crosshead speed of 300 mm/minute. Note that tensile strength and elongation at break are the average of the values at fracture (maximum point).
[Table 1-1]
 Draft ratioDrawing temperatureDraw ratioRelaxation temperatureRelaxation rate
(-)(°C)(times)(°C)(%)
Example 1 120 80 4.50 130 0
Example 2 120 130 4.25 130 0
Example 3 120 130 3.50 130 0
Reference Example 4 120 130 3.00 130 0
Example 5 60 100 5.50 100 0
Example 6 120 130 4.25 150 10
Comparative Example 1 2550 - - - -
Comparative Example 2 2550 144 1.16 144 0
Comparative Example 3 10000 - - - -
Comparative examle 4 850 - - - -
[Table 1-2]
 Fiber diameterBirefringenc eDegree of crystal orientationCrystal sizeTm1Tm2Tensile strengthElongation at break
(µm)(× 10-3)(%)(nm)(°C)(°C)(cN/dtex)(%)
Example 1 18.9 63.7 96.4 5.01 164.9 172.1 4.3 14
Example 2 19.2 53.4 97.2 6.12 164.9 172.2 4.6 15
Example 3 20.6 49.5 96.8 6.60 165.1 175.1 3.5 24
Reference Example 4 22.4 46.6 95.5 9.01 - 175.1 2.6 42
Example 5 24.0 53.4 97.6 4.82 164.9 172.1 4.9 15
Example 6 Comparative Example 1 19.5 56.3 97.0 8.97 164.9 172.1 5.1 21
40.0 48.0 94.2 14.08 - 191.0 3.8 30
Comparative Example 2 40.0 58.0 93.7 14.02 - 191.0 4.2 13
Comparative Example 3 20.0 59.0 95.7 13.85 - 190.1 4.0 21
Comparative example 4 28.7 32.8 86.4 12.13 - 170.1 1.7 153

Industrial Applicability



[0098] The vinylidene fluoride resin fiber according to the present invention may be used in various formats such as woven fabrics, knits, strings, cut fibers, papers, and nonwoven fabrics, and in various industrial materials such as reinforced fibers for hollow fiber membranes, ropes and clothes, in base materials for medical use, in colored fibers, and in sensor devices as a piezoelectric substance.


Claims

1. A vinylidene fluoride resin fiber comprising a plurality of vinylidene fluoride resin filaments, wherein

the fiber has a degree of crystal orientation of not less than 80% and a crystal size of not greater than 12 nm as determined on the basis of X-ray diffraction from an azimuth angle intensity distribution curve of 2θ = 20.8 ± 1° as described in the description,

the vinylidene fluoride resin has two or more melting peaks within a range of 150°C to 180°C, determined as described in the description, and

an average birefringence, determined as described in the description, is not less than 30 × 10-3.


 
2. The vinylidene fluoride resin fiber according to claim 1, wherein a diameter of the filament is not less than 5 µm and less than 80 µm.
 
3. The vinylidene fluoride resin fiber according to claim 1 or 2, wherein the vinylidene fluoride resin is a homopolymer of a vinylidene fluoride monomer.
 
4. The vinylidene fluoride resin fiber according to claim 1 or 2, wherein

the vinylidene fluoride resin is a vinylidene fluoride copolymer of a vinylidene fluoride monomer and another monomer, and

the other monomer is at least one type selected from the group consisting of hexafluoropropylene, trifluoroethylene, tetrafluoroethylene, and chlorotrifluoroethylene.


 
5. The vinylidene fluoride resin fiber according to claim 4, wherein the vinylidene fluoride copolymer contains not less than 90 mol% of a vinylidene fluoride monomer.
 
6. The vinylidene fluoride resin fiber according to any one of claims 1 to 5, wherein an inherent viscosity of the vinylidene fluoride resin, determined as described in the description, is from 0.70 dL/g to 0.95 dL/g.
 
7. The vinylidene fluoride resin fiber according to any one of claims 1 to 6, wherein a tensile strength, determined as described in the description, is not less than 2.0 cN/dtex and an elongation at break, determined as described in the description, is not greater than 50%.
 
8. The vinylidene fluoride resin fiber according to any one of claims 1 to 7, wherein the average birefringence, determined as described in the description, is not less than 40 × 10-3, a tensile strength, determined as described in the description, is not less than 3.1 cN/dtex, and a elongation at break, determined as described in the description, is not greater than 40%.
 
9. A sheet-like structure comprising the vinylidene fluoride resin fiber described in any one of claims 1 to 8.
 
10. The sheet-like structure according to claim 9, wherein the structure is formed in a mesh form.
 


Ansprüche

1. Vinylidenfluoridharzfaser, umfassend eine Vielzahl von Vinylidenfluoridharzfilamenten, wobei

die Faser einen Kristallorientierungsgrad von nicht weniger als 80 % und eine Kristallgröße von nicht mehr als 12 nm aufweist, ermittelt auf der Grundlage der Röntgenbeugung aus einer Azimutwinkelintensitätsverteilungskurve von 2θ = 20,8 ± 1°, wie in der Beschreibung beschrieben,

das Vinylidenfluoridharz zwei oder mehr Schmelzpeaks innerhalb eines Bereichs von 150 °C bis 180 °C aufweist, ermittelt wie in der Beschreibung beschrieben, und

eine durchschnittliche Doppelbrechung, ermittelt wie in der Beschreibung beschrieben, die nicht weniger als 30 × 10-3 beträgt.


 
2. Vinylidenfluoridharzfaser nach Anspruch 1, wobei ein Durchmesser des Filaments nicht weniger als 5 µm und weniger als 80 µm beträgt.
 
3. Vinylidenfluoridharzfaser nach Anspruch 1 oder 2, wobei das Vinylidenfluoridharz ein Homopolymer eines Vinylidenfluoridmonomers ist.
 
4. Vinylidenfluoridharzfaser nach Anspruch 1 oder 2, wobei

das Vinylidenfluoridharz ein Vinylidenfluoridcopolymer eines Vinylidenfluoridmonomers und eines anderen Monomers ist, und

das andere Monomer mindestens ein Typ ist, der aus der Gruppe ausgewählt ist, bestehend aus Hexafluorpropylen, Trifluorethylen, Tetrafluorethylen und Chlortrifluorethylen.


 
5. Vinylidenfluoridharzfaser nach Anspruch 4, wobei das Vinylidenfluoridcopolymer nicht weniger als 90 Mol-% eines Vinylidenfluoridmonomers enthält.
 
6. Vinylidenfluoridharzfaser nach einem der Ansprüche 1 bis 5, wobei eine inhärente Viskosität des Vinylidenfluoridharzes, ermittelt wie in der Beschreibung beschrieben, von 0,70 dL/g bis 0,95 dL/g beträgt.
 
7. Vinylidenfluoridharzfaser nach einem der Ansprüche 1 bis 6, wobei eine Zugfestigkeit, ermittelt wie in der Beschreibung beschrieben, nicht weniger als 2,0 cN/dtex beträgt und eine Bruchdehnung, ermittelt wie in der Beschreibung beschrieben, nicht mehr als 50 % beträgt.
 
8. Vinylidenfluoridharzfaser nach einem der Ansprüche 1 bis 7, wobei die durchschnittliche Doppelbrechung, ermittelt wie in der Beschreibung beschrieben, nicht weniger als 40 × 10-3 beträgt, eine Zugfestigkeit, ermittelt wie in der Beschreibung beschrieben, nicht weniger als 3,1 cN/dtex beträgt, und eine Bruchdehnung, ermittelt wie in der Beschreibung beschrieben, nicht mehr als 40 % beträgt.
 
9. Blattförmige Struktur, umfassend die in einem der Ansprüche 1 bis 8 beschriebene Vinylidenfluoridharzfaser.
 
10. Blattförmige Struktur nach Anspruch 9, wobei die Struktur in einer Maschenform ausgebildet ist.
 


Revendications

1. Fibre de résine de fluorure de vinylidène comprenant une pluralité de filaments de résine de fluorure de vinylidène, dans laquelle

la fibre a un degré d'orientation cristalline qui n'est pas inférieur à 80 % et une dimension cristalline ne dépassant pas 12 nm telle que déterminée sur la base d'une diffraction des rayons X à partir d'une courbe de distribution d'intensité d'angle azimutal de 2θ = 20,8 ± 1° comme décrit dans la description,

la résine de fluorure de vinylidène a deux pics de fusion ou plus dans une plage de 150 °C à 180 °C, déterminés de la façon décrite dans la description, et

une biréfringence moyenne, déterminée de la façon décrite dans la description, n'est pas inférieure à 30 × 10-3.


 
2. Fibre de résine de fluorure de vinylidène selon la revendication 1, dans laquelle un diamètre du filament n'est pas inférieur à 5 µm et est inférieur à 80 µm.
 
3. Fibre de résine de fluorure de vinylidène selon la revendication 1 ou 2, dans laquelle la résine de fluorure de vinylidène est un homopolymère d'un monomère fluorure de vinylidène.
 
4. Fibre de résine de fluorure de vinylidène selon la revendication 1 ou 2, dans laquelle

la résine de fluorure de vinylidène est un copolymère de fluorure de vinylidène d'un monomère fluorure de vinylidène et d'un autre monomère, et

l'autre monomère est au moins un type choisi dans le groupe constitué d'hexafluoropropylène, trifluoroéthylène, tétrafluoroéthylène, et chlorotrifluoroéthylène.


 
5. Fibre de résine de fluorure de vinylidène selon la revendication 4, dans laquelle le copolymère de fluorure de vinylidène ne contient pas moins de 90 % molaires d'un monomère fluorure de vinylidène.
 
6. Fibre de résine de fluorure de vinylidène selon l'une quelconque des revendications 1 à 5, dans laquelle une viscosité inhérente de la résine de fluorure de vinylidène, déterminée de la façon décrite dans la description, va de 0,70 dL/g à 0,95 dL/g.
 
7. Fibre de résine de fluorure de vinylidène selon l'une quelconque des revendications 1 à 6, dans laquelle une résistance à la traction, déterminée de la façon décrite dans la description, n'est pas inférieure à 2,0 cN/dtex et un allongement à la rupture, déterminé de la façon décrite dans la description, n'est pas supérieur à 50 %.
 
8. Fibre de résine de fluorure de vinylidène selon l'une quelconque des revendications 1 à 7, dans laquelle la biréfringence moyenne, déterminée de la façon décrite dans la description, n'est pas inférieure à 40 × 10-3, une résistance à la traction, déterminée de la façon décrite dans la description, n'est pas inférieure à 3,1 cN/dtex, et un allongement à la rupture, déterminé de la façon décrite dans la description, n'est pas supérieur à 40 %.
 
9. Structure de type feuille comprenant la fibre de résine de fluorure de vinylidène décrite dans l'une quelconque des revendications 1 à 8.
 
10. Structure de type feuille selon la revendication 9, dans laquelle la structure est formée sous une forme de treillis.
 






Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description




Non-patent literature cited in the description