Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N30/00—Piezoelectric or electrostrictive devices
  • H10N30/80—Constructional details
  • H10N30/85—Piezoelectric or electrostrictive active materials
  • H10N30/857—Macromolecular compositions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F14/18—Monomers containing fluorine
  • C08F14/22—Vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N30/00—Piezoelectric or electrostrictive devices
  • H10N30/01—Manufacture or treatment
  • H10N30/09—Forming piezoelectric or electrostrictive materials
  • H10N30/098—Forming organic materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride

Definitions

• the present invention relates to a composition for forming a polyvinylidene fluoride film.
• PVDF Polyvinylidene fluoride
• the ⁇ -type crystallization rate ( ⁇ crystallization rate) of PVDF is improved by forming a PVDF film on a substrate using a PVDF solution containing aluminum nitrate nonahydrate and magnesium nitrate hexahydrate.
• the improvement of the ferroelectric property and the piezoelectric property is expected due to the improvement of the ⁇ crystallization rate, and therefore further improvement is required.
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a PVDF film-forming composition that gives a PVDF film having a high ⁇ crystallization rate, and a PVDF film obtained from the composition.
• the present inventors have found that a composition containing PVDF, a predetermined surfactant and a solvent gives a PVDF film having a high ⁇ crystallization rate. Then, the present invention was completed.
• the present invention provides the following composition for forming a polyvinylidene fluoride film and a polyvinylidene fluoride film.
• Composition for forming polyvinylidene fluoride film comprising polyvinylidene fluoride, at least one surfactant selected from a sulfuric acid type surfactant, a sulfonic acid type surfactant and a quaternary ammonium salt type surfactant, and a solvent .. 2.
• the polyvinylidene fluoride film of 4 wherein the polyvinylidene fluoride film contains a ⁇ -type crystal structure. 6.
• the polyvinylidene fluoride film of 5 wherein the ⁇ -type crystallization rate of the polyvinylidene fluoride is 70% by mass or more.
• 7. A method for producing a polyvinylidene fluoride film, which comprises heat treating at 55 to 105° C. when the polyvinylidene fluoride film is formed using the composition for forming a polyvinylidene fluoride film according to any one of 1 to 3.
• the PVDF film-forming composition of the present invention provides a PVDF film having a high ⁇ crystallization rate.
• the PVDF film-forming composition of the present invention comprises PVDF, at least one surfactant selected from a sulfuric acid type surfactant, a sulfonic acid type surfactant and a quaternary ammonium salt type surfactant, and a solvent. Including.
• the PVDF preferably has a predetermined viscosity, and examples thereof include those having the following viscosities.
• the intrinsic viscosity measured according to ISO 1060-1 is preferably 0.5 to 4.0 dl/g, more preferably 0.7 to 1.5 dl/g.
• the surfactant includes at least one selected from a sulfuric acid type surfactant, a sulfonic acid type surfactant and a quaternary ammonium salt type surfactant.
• the sulfuric acid type surfactant and the sulfonic acid are used. It is preferable to include at least one selected from surface-active agents.
• sulfuric acid surfactants include alkyl sulfates.
• the alkyl group contained in these surfactants preferably has 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms.
• Specific examples include sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, lithium dodecyl sulfate, and the like.
• sulfonic acid type surfactants examples include alkyl sulfonates and alkylbenzene sulfonates.
• the alkyl group contained in these surfactants preferably has 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms.
• Specific examples include sodium 1-decane sulfonate, sodium dodecylbenzene sulfonate, and the like.
• Examples of the quaternary ammonium salt type surfactant include alkyl trimethyl ammonium salt.
• the alkyl group contained in these surfactants preferably has 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms. Specific examples include hexadecyltrimethylammonium bromide and the like.
• the blending amount of the surfactant is preferably 0.001 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of PVDF.
• the solvent is not particularly limited as long as it can dissolve PVDF and a surfactant.
• a solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide, N-methyl-2-pyrrolidone, triethyl phosphate, tetrahydrofuran, cyclopentyl methyl ether, ⁇ -butyrolactone, cyclopentanone, cyclohexanone, 3- Methylcyclohexanone, isophorone, menthone, propylene carbonate, ethylene carbonate, trichloroethane, chlorodifluoromethane, acetone, methyl ethyl ketone, methyl amyl ketone, acetonitrile, N,N-dimethylacetamide, hexamethylphosphoramide, tetramethylurea, ethyl acetate, acetic acid , Pyridine, butyl acetate, polyethylene glycol methyl
• DMF, acetone, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and methyl ethyl ketone are preferred, DMF and acetone are more preferred, and a mixed solvent of DMF and acetone is even more preferred.
• the solvent may be used alone or in combination of two or more.
• the amount of the solvent used is preferably 400 to 99,900 parts by mass, more preferably 900 to 19,900 parts by mass, and more preferably 900 to 9,900 parts by mass with respect to 100 parts by mass of PVDF. More preferable.
• the crystallinity of the PVDF film obtained by using the PVDF film-forming composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more in the total PVDF. When the crystallinity is 50% by mass or more, better ferroelectricity and piezoelectric properties are expected.
• the upper limit of the crystallinity is 100% by mass, but it is usually about 60% by mass.
• the ⁇ crystallization rate of PVDF in the PVDF film is preferably 50% by mass or more, more preferably 65% by mass or more, and even more preferably 75% by mass or more in the crystallized PVDF.
• the upper limit of the ⁇ crystallization rate is 100% by mass, but it is usually about 90% by mass.
• a known method can be adopted, and solvent casting method, doctor blade method, spin coating method, electrospinning method, slit coater, roll coater, inkjet, dip Examples include coat and screen printing.
• a heat treatment may be performed to accelerate drying and crystallization, if necessary.
• the heating temperature at this time is preferably 55 to 105°C, more preferably 60 to 100°C.
• the heating time is preferably 1 to 240 minutes, more preferably 5 to 30 minutes. This heat treatment can increase the ⁇ crystallization rate.
• Examples of the equipment used for heating in the heat treatment include a hot plate and an oven.
• the heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.
• the thickness of the PVDF film is usually about 50 nm to 50 ⁇ m, preferably about 100 nm to 20 ⁇ m, more preferably about 1 to 10 ⁇ m.
• the film thickness can be adjusted by adjusting the concentration of the composition, film forming conditions and the like.
• the film thickness can be measured with a micrometer, a step gauge (fine shape measuring instrument), or the like.
• PVDF1 “Kynar 721” manufactured by Arkema Ltd., measured according to ASTM D3835, melt temperature 232° C., shear rate 100 sec ⁇ 1 melt viscosity 4.0-8.0 Kpoise.
• PVDF2 “KF polymer 850” manufactured by Kureha Co., Ltd., intrinsic viscosity 0.85 dl/g measured according to ISO 1060-1.
• composition A1 100 parts by mass of PVDF1 were added to 450 parts by mass of DMF (manufactured by Junsei Chemical Co., Ltd.) and acetone (manufactured by Junsei Chemical Co., Ltd.). was dissolved in a mixed solvent of 450 parts by weight of sodium dodecyl sulfate (Tokyo Kasei Kogyo Co., Ltd., C 12 H 25 SO 4 Na ) was added 10 parts by weight, and stirred to dissolve until uniform .. Then, the obtained solution was filtered with a syringe filter (5 ⁇ m) to obtain a composition A1.
• composition B1 was prepared in the same manner as in Example 1-1, except that the amount of sodium dodecyl sulfate mixed was changed to 7 parts by mass.
• composition C1 was prepared in the same manner as in Example 1-1, except that the compounding amount of sodium dodecyl sulfate was changed to 5 parts by mass.
• composition D1 was prepared in the same manner as in Example 1-1, except that the compounding amount of sodium dodecyl sulfate was changed to 3 parts by mass.
• composition E1 was prepared in the same manner as in Example 1-1, except that the compounding amount of sodium dodecyl sulfate was changed to 1 part by mass.
• composition F1 was prepared in the same manner as in Example 1-1, except that sodium dodecyl sulfate was not added.
• composition A2 100 parts by mass of PVDF2 was dissolved in a mixed solvent of 950 parts by mass of DMF and 950 parts by mass of acetone, and then 10 parts by mass of sodium dodecyl sulfate was added and stirred until uniform. And dissolved. Then, the obtained solution was filtered with a syringe filter (5 ⁇ m) to obtain a composition A2.
• composition B2 was prepared in the same manner as in Example 1-6, except that the blending amount of sodium dodecyl sulfate was changed to 7 parts by mass.
• composition C2 was prepared in the same manner as in Example 1-6, except that the blending amount of sodium dodecyl sulfate was changed to 5 parts by mass.
• composition D2 was prepared in the same manner as in Example 1-6, except that the compounding amount of sodium dodecyl sulfate was changed to 3 parts by mass.
• composition E2 was prepared in the same manner as in Example 1-6, except that the amount of sodium dodecyl sulfate added was changed to 0.02 g.
• composition F2 was prepared in the same manner as in Example 1-6 except that sodium dodecyl sulfate was not added.
• Example 1-11 Preparation of Composition G After dissolving 100 parts by mass of PVDF2 in a mixed solvent of 950 parts by mass of DMF and 950 parts by mass of acetone, sodium tetradecyl sulfate (Fuji Film Wako Pure Chemical Industries, Ltd., C 14 H 29 SO 4 Na) (10 parts by mass) was added, and the mixture was stirred until it became homogeneous and dissolved. Then, the obtained solution was filtered with a syringe filter (5 ⁇ m) to obtain a composition G.
• sodium tetradecyl sulfate Fruji Film Wako Pure Chemical Industries, Ltd., C 14 H 29 SO 4 Na
• composition H Example 1-13 except that sodium tetradecyl sulfate was changed to sodium hexadecyl sulfate (F16 Film Wako Pure Chemical Industries, Ltd., C 16 H 33 SO 4 Na).
• Composition H was prepared in a similar manner.
• Example 1-13 Composition I Preparation sodium tetradecyl sodium octadecyl sulfate (Fujifilm manufactured by Wako Pure Chemical Industries, Ltd., C 18 H 37 SO 4 Na ) was changed to the Example 1-13 Composition I was prepared in a similar manner.
• composition J Preparation tetradecyl sulfate sodium lithium dodecyl sulfate (Fujifilm manufactured by Wako Pure Chemical Industries, Ltd., C 12 H 25 SO 4 Li ) was changed to the Example 1-13 Composition J was prepared in a similar manner.
• composition K Example 1-13 except that sodium tetradecyl sulfate was changed to sodium 1-decanesulfonate (manufactured by Tokyo Kasei Kogyo Co., Ltd., C 10 H 21 SO 3 Na).
• Composition K was prepared in the same manner as in.
• Example 1-16 Preparation of Composition L Except that sodium tetradecyl sulfate was changed to hexadecyltrimethylammonium bromide ([C 16 H 33 N(CH 3 ) 3 ]Br manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) A composition L was prepared in the same manner as in Example 1-13.
• composition M Preparation of composition M In the same manner as in Example 1-13 except that sodium tetradecyl sulfate was changed to sodium laurate (C 11 H 23 COONa manufactured by Tokyo Chemical Industry Co., Ltd.). Composition M was prepared.
• composition N Sodium tetradecyl sulfate was changed to sodium N-dodecanoylsarcosinate (C 11 H 23 CON(CH 3 )CH 2 COONa manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). Composition N was prepared in the same manner as in Example 1-13 except for that.
• composition O Example 1-13 except that sodium tetradecyl sulfate was changed to sodium monododecyl phosphate (C 12 H 25 PO 4 Na 2 manufactured by Tokyo Kasei Kogyo Co., Ltd.).
• Composition O was prepared in the same manner as in.
• Composition P Sodium tetradecyl sulfate was changed to dodecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt (C 17 H 37 NO 3 S manufactured by Tokyo Chemical Industry Co., Ltd.). Composition P was prepared in the same manner as in Example 1-13 except for the above.
• Example 2-1 Production of PVDF membrane
• 300 ⁇ L of the composition A1 obtained in Example 1-1 was dropped on a Petri dish ( ⁇ 35 mm) to spread the solution uniformly.
• the petri dish was heat-treated for 5 minutes on a hot plate heated to 80° C. to dry and crystallize, thereby obtaining a self-supporting film a1 made of PVDF and having a film thickness of about 10 ⁇ m.
• Example 2- Example 2-Except that compositions C1, D1 and E1 obtained in Examples 1-3 to 1-5 and F1 obtained in Comparative Example 1-1 were respectively used instead of the composition A1 In the same manner as in No. 1, self-supporting films c1, d1, e1 and f1 made of PVDF and having a film thickness of about 10 ⁇ m were obtained.
• Example 3-1 The composition A2 obtained in Example 1-6 was dropped on a glass substrate (100 mm square), and a coating film was formed using a doctor blade (liquid thickness 100 ⁇ m). Next, the obtained coating film was heat-treated on a hot plate heated at 80° C. for 10 minutes to be dried and crystallized to obtain a self-supporting film a2 made of PVDF and having a film thickness of about 3 ⁇ m.
• Example 3- Example 3-Except that compositions B2, C2 and D2 obtained in Examples 1-7 to 1-9 and F2 obtained in Comparative Example 1-2 were used instead of the composition A2, respectively.
• free-standing films b2, c2, d2 and f2 made of PVDF and having a film thickness of about 3 ⁇ m were obtained.
• Example 4-1 The composition A2 obtained in Example 1-6 was dropped on a silicon substrate to form a coating film by spin coating (990 rpm, 20 sec). Next, the obtained coating film was heat-treated on a hot plate heated to 80° C. for 10 minutes to be dried and crystallized to obtain a film a3 made of PVDF and having a film thickness of 500 nm.
• Example 4 Example 4-Except that compositions B2, C2 and D2 obtained in Examples 1-7 to 1-9 and F2 obtained in Comparative Example 1-2 were used instead of the composition A2, respectively. Films b3, c3, d3 and f3 made of PVDF and having a thickness of 500 nm were obtained in the same manner as in 1.
• Example 5-1 The composition G obtained in Example 1-11 was dropped onto a Petri dish ( ⁇ 35 mm) in an amount of 300 ⁇ L to spread the solution uniformly.
• the petri dish was heat-treated on a hot plate heated to 80° C. for 5 minutes to be dried and crystallized to obtain a self-supporting film g made of PVDF and having a film thickness of about 10 ⁇ m.
• Examples 5-2 to 5-6, Comparative Examples 5-1 to 5-4 instead of the composition G, the compositions H, I, J, K and L obtained in Examples 1-12 to 1-16 and the composition M obtained in Comparative Examples 1-3 to 1-6, respectively. , N, O and P were used, a self-supporting film h, i, j, k, l, m, n, o of PVDF having a film thickness of about 10 ⁇ m was prepared in the same manner as in Example 5-1. got p.
• Example 6-1 The composition A2 obtained in Example 1-6 was dropped onto a Petri dish ( ⁇ 35 mm) in an amount of 300 ⁇ L to uniformly spread the solution.
• the petri dish was heat-treated on a hot plate heated to 60° C. for 5 minutes to be dried and crystallized to obtain a self-supporting film a4 made of PVDF and having a film thickness of about 10 ⁇ m.
• Examples 6-2 to 6-5, Comparative Examples 6-1 to 6-4 A film thickness made of PVDF in the same manner as in Example 6-1 except that the heat treatment temperatures were changed to 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., 140° C. Approximately 10 ⁇ m self-supporting films a5 to a12 were obtained.
• a alpha absorbance at 761cm -1
• a ⁇ absorbance at 840 cm -1
• K alpha extinction coefficient at 761cm -1 (6.1 ⁇ 10 4 cm 2 mol -1)
• K beta extinction coefficient at 840cm -1 (7.7 ⁇ 10 4 cm 2 mol -1)
• a Fourier transform infrared spectrophotometer 2 (“Nicolet iS5" manufactured by Thermo Fisher Scientific Co., Ltd.) was used without peeling the film from the silicon substrate, and the measurement range was: The absorbance in the thickness direction of the object to be measured was measured under the conditions of 700-4000 cm ⁇ 1 , the number of scans: 32 times, and the resolution: 8 cm ⁇ 1 .
• the above formula was used as the calculation formula.

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