WO2017221985A1 - 二軸延伸ポリプロピレンフィルム、金属化フィルム、及び、コンデンサ - Google Patents
二軸延伸ポリプロピレンフィルム、金属化フィルム、及び、コンデンサ Download PDFInfo
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- WO2017221985A1 WO2017221985A1 PCT/JP2017/022896 JP2017022896W WO2017221985A1 WO 2017221985 A1 WO2017221985 A1 WO 2017221985A1 JP 2017022896 W JP2017022896 W JP 2017022896W WO 2017221985 A1 WO2017221985 A1 WO 2017221985A1
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- WIPO (PCT)
- Prior art keywords
- polypropylene
- film
- molecular weight
- less
- resin
- Prior art date
Links
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Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
Definitions
- the present invention relates to a biaxially stretched polypropylene film with improved dielectric breakdown strength (ES).
- the present invention also relates to a metallized film having the biaxially stretched polypropylene film and a capacitor.
- biaxially stretched polypropylene films are used in electronic and electrical equipment, and because of their excellent electrical properties such as voltage resistance and low dielectric loss properties, and high moisture resistance, for example, high voltage capacitors, various switching power supplies, It is widely used as a dielectric film for capacitors such as capacitors for filters and smoothing capacitors such as converters and inverters.
- Patent Document 1 discloses a method for producing a biaxially stretched polypropylene film for capacitors, and describes that polypropylene having a long-chain branched structure or a crosslinked structure is contained in a polypropylene resin.
- the polypropylene having the above-mentioned long chain branched structure or cross-linked structure is a method of forming a partial cross-linked structure by a method such as electron beam irradiation in the post-polymerization process of the resin, or adding a crosslinking assistant and a peroxide to the polypropylene. It is described that a long chain branched structure or a crosslinked structure is introduced into the molecular chain by the kneading method.
- Patent Document 2 discloses a metallized biaxially oriented polypropylene film made of a polypropylene resin in which a linear polypropylene is mixed with a branched polypropylene having a melt tension and a melt flow index at a specific temperature satisfying a specific relational expression. Disclosed and obtained as a branched polypropylene by electron beam cross-linking method (Profax PF-814 manufactured by Basell) or obtained by cross-linking modification with peroxide [Daploy HMS-PP manufactured by Borealis (WB130HMS, WB135HMS) )] Can be used.
- PF-814 electron beam cross-linking method
- Borealis WB130HMS, WB135HMS
- Patent Document 3 discloses a biaxially stretched polypropylene film for a capacitor containing a specific amount of branched polypropylene, and obtained as a branched polypropylene by an electron beam cross-linking method (Profax PF-814 manufactured by Basell). ) And those obtained by cross-linking modification with peroxides (Daploy HMS-PP (WB130HMS, WB135HMS) manufactured by Borealis) can be used.
- Patent Document 4 discloses an invention relating to a polypropylene film for a capacitor obtained by biaxially stretching a polypropylene resin.
- the long-chain branched polypropylene can be included in the polypropylene resin, and Profax PF manufactured by Basell as a long-chain branched polypropylene.
- Borealis Daploy HMS-PP WB130HMS, WB135HMS and WB140HMS
- JP 2007-84813 A JP 2007-290380 A JP 2011-122142 A JP 2014-231484 A
- Patent Document 1 has an effect of improving the stretchability of a polypropylene film by adding or containing a polypropylene resin having a long-chain branched structure or a crosslinked structure to a highly stereoregular polypropylene resin. Is disclosed.
- Patent Document 2 by mixing specific branched polypropylene with linear polypropylene, the size of the spherulite generated in the cooling process of the melt-extruded resin sheet can be controlled to be small, and the insulation defects generated in the stretching process can be reduced. The effect that generation can be suppressed low is disclosed.
- the branched polypropylene has a function of ⁇ crystal nucleating agent, and can form a rough surface by crystal transformation within the range of addition in a small amount, and coupled with the effect of reducing the spherulite size described above, There is also disclosed an effect that a biaxially oriented polypropylene film having a surface roughness that is small in size, can be formed densely, has excellent projection uniformity, and also has an excellent balance of roughness density is obtained. .
- the polypropylene film contains a branched polypropylene in a specific amount, so that the spherulite size generated in the cooling process of the melt-extruded resin sheet can be controlled to be smaller easily and is generated in the stretching process.
- generation of an insulation defect can be suppressed small and the polypropylene film excellent in withstand voltage property can be obtained is disclosed.
- the branched polypropylene has the effect of reducing the above spherulite size by enabling the formation of a rough surface by crystal transformation if it is added in a certain range while having the action of an ⁇ crystal nucleating agent.
- the biaxially stretched polypropylene film can be obtained with a small and dense size, excellent uniformity of the projection, and excellent surface roughness without coarse projection. It is disclosed.
- Patent Document 4 by including a long-chain branched polypropylene in a polypropylene resin, the crystallite size obtained from the ⁇ -crystal (040) reflecting surface of the polypropylene is reduced, the birefringence is increased, and the surface roughness is increased. It is disclosed that the withstand voltage can be improved over a long period of time by making the size smaller.
- the polypropylene resin having a long chain branched structure or a crosslinked structure obtained by electron beam crosslinking or peroxide modification described in Patent Documents 1 to 3 is caused by crosslinking and modification in the subsequent step of resin polymerization. It has been found that there is a problem that a film excellent in dielectric breakdown strength (ES) cannot be obtained due to a large number of gel components that become insulation defects.
- ES dielectric breakdown strength
- the polypropylene resin having a long-chain branched structure or a crosslinked structure obtained by electron beam crosslinking or peroxide modification is not compatible with linear polypropylene because the branch chain length and the branch chain interval are not appropriate. Also, since a uniform composition and film surface shape cannot be obtained from a dry blend with linear polypropylene, it has also been found that the problem of difficulty in improving the strength of dielectric breakdown (ES) as in Patent Document 3 is found. It was.
- an object of the present invention is to provide a biaxially stretched polypropylene film having excellent dielectric breakdown strength (ES).
- the present inventors include polypropylene A having a strain hardening parameter of less than 3 and polypropylene B having a strain hardening parameter of 3 or more and 20 or less as resin components. It has been found that the above problems can be solved by using an axially stretched polypropylene film, and the present invention has been completed.
- the present invention includes the following aspects.
- Polypropylene A having a strain hardening parameter of less than 3 A biaxially stretched polypropylene film comprising, as a resin component, polypropylene B having a strain hardening parameter of 3 or more and 20 or less.
- polypropylene B having a strain hardening parameter of 3 or more and 20 or less.
- the gel fraction of the polypropylene B is 1000 ppm by mass or less based on the mass of the polypropylene B” means “the gel fraction of the polypropylene B is 1000 by mass when the entire polypropylene B is used as a whole. It means “below ppm by mass”.
- [4] The biaxially stretched polypropylene film according to any one of [1] to [3], wherein the polypropylene B is obtained by polymerizing propylene using a metallocene catalyst.
- polypropylene A having a strain hardening parameter of less than 3 and polypropylene B having a strain hardening parameter of 3 or more and 20 or less as a resin component of a biaxially stretched polypropylene film, A biaxially stretched polypropylene film having excellent strength can be obtained.
- FIG. 1 shows a conceptual diagram of the curability parameter ( ⁇ ).
- the film according to this embodiment contains a polypropylene A having a strain hardening parameter of less than 3 and a polypropylene B having a strain hardening parameter of 3 or more and 20 or less as a resin component. It is a film.
- G ′ ( ⁇ ) is the storage modulus as a function of angular velocity ⁇
- G ′ ( ⁇ / 2) is the storage modulus as a function of ⁇ / 2
- G ′′ ( ⁇ ) is a function of each velocity ⁇ .
- Loss modulus G ′′ ( ⁇ / 2) is the loss modulus as a function of ⁇ / 2
- t is time.
- the method for obtaining the strain hardenability parameter is an outline, and details of the method for obtaining the strain hardenability parameter are described in the [Example] section of this specification.
- the strain hardening parameter ( ⁇ ) thus obtained is a parameter that captures a phenomenon called a strain hardening phenomenon, in which the elongational viscosity rapidly grows with time when a certain strain is exceeded.
- a strain hardening phenomenon in which the elongational viscosity rapidly grows with time when a certain strain is exceeded.
- the strain hardenability parameter is large, the strain hardenability is large and the resistance to elongation deformation is large, that is, the degree of entanglement of molecular chains is large.
- the strain hardening parameter is small, the strain hardening is small and the degree of molecular chain entanglement is small.
- the strain hardening phenomenon is observed in a polymer having a branch, and occurs because the internal strain of a molecular chain, particularly a molecular chain segment between branch points, greatly increases according to the external strain due to inhibition of molecular contraction.
- the stress generated by the compression of the branch segment also contributes to strain hardening. Therefore, the strain hardening parameter is different in the case where only the branched structure of the polymer is different, and the Molecular Stress Function (MSF) theory [W. H. Wagner, M.M. Yamaguchi, M .; Takahashi, J. et al. Rheol. , Vol. 47, p. 779 (2003)] greatly varies depending on the length of the branched chain, and increases when the branched chain is long.
- MSF Molecular Stress Function
- the unsteady uniaxial extensional viscosity function ⁇ E (t) can be measured at an arbitrary strain rate using a uniaxial extensional viscosity measuring apparatus.
- the shear viscoelasticity can be measured using a dynamic viscoelasticity measuring device such as a rheometer.
- the biaxially stretched polypropylene film is excellent in the strength of dielectric breakdown when used for a capacitor for the following reason.
- the reason why the biaxially stretched polypropylene film is excellent in the above effect is clearly described here as being within the scope of the present invention even if it is different from the following reason.
- Polypropylene having a strain hardening parameter (non-linearity parameter) of less than 3 means that there is almost no strain hardening property of elongational viscosity, and a mechanically weak part such as a thin part of the sheet is likely to be locally deformed.
- the strain hardening parameter of polypropylene A is preferably 2.5 or less, more preferably 2.0 or less, further preferably 1.5 or less, and particularly preferably 1.2 or less. If the strain hardening parameter of polypropylene A is the above, it is preferable because a good moldability can be obtained and a film having excellent mechanical strength can be obtained.
- the lower limit value of the strain hardening parameter is usually 1. Therefore, the strain hardening parameter of polypropylene A is 1 or more.
- entanglement between molecular chains appears remarkably at a high take-up speed, and melt fracture during forming tends to occur.
- the gel fraction in polypropylene A is preferably 1000 ppm by mass or less, more preferably 800 ppm by mass or less, still more preferably relative to the mass of polypropylene A in the resin component (by mass when polypropylene A is used as a whole). Is 500 mass ppm or less, more preferably 200 mass ppm or less, and particularly preferably 100 mass ppm or less. Moreover, the smaller the gel fraction of polypropylene A, the better. Therefore, the lower limit is not particularly limited, but is, for example, 0 mass ppm, 1 mass ppm, or the like.
- the gel fraction is the mass ratio of the gel component in the resin.
- the gel component refers to a polymer having a network structure formed by crosslinking the polymer. If the gel fraction in polypropylene A is 1000% by mass or less, insulation defects in the film are reduced, and a biaxially stretched polypropylene film superior in dielectric breakdown strength can be obtained.
- the gel fraction was measured as follows. (1) About 1 g of a weighed sample was put into 200 mL of xylene and heated at 120 ⁇ 5 ° C. for 12 hours. (2) The obtained liquid was filtered through a weighed 200 mesh wire mesh. (3) The filtered mesh was dried at room temperature for 8 hours and at 80 ° C. for 3 hours. (4) The filtered mesh was weighed and the ratio of the residue was taken as the gel fraction.
- the weight average molecular weight (Mw) of polypropylene A is preferably 250,000 to 450,000, more preferably 250,000 to 400,000.
- Mw weight average molecular weight
- the resin fluidity is appropriate, the thickness of the cast raw sheet is easily controlled, and a thin stretched film can be easily produced. Can be. Furthermore, it becomes difficult to generate unevenness in the thickness of the sheet and film, and the sheet can have appropriate stretchability, which is preferable.
- the molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn)) of polypropylene A is preferably 7.0 or more and 12.0 or less, more preferably 7.5 or more and 12.0 or less, and further preferably 7.5. It is 11.0 or less and particularly preferably 8.0 or more and 10.0 or less.
- the molecular weight distribution (Z average molecular weight / number average molecular weight (Mz / Mn)) of polypropylene A is more preferably 25.0 or more and 60.0 or less, and further preferably 25.0 or more and 50.0 or less. Preferably they are 40.0 or more and 50.0 or less.
- the weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight and molecular weight distribution (Mw / Mn and Mz / Mn) of polypropylene A can be measured using a gel permeation chromatograph (GPC) apparatus. It can. In the present invention, the measurement was carried out using HLC-8121GPC-HT (trade name) manufactured by Tosoh Corporation and a differential refractometer (RI) built-in type high temperature GPC measuring machine. As the GPC column, three TSKgel GMHHR-H (20) HT manufactured by Tosoh Corporation were connected and used.
- GPC gel permeation chromatograph
- the column temperature was set to 140 ° C., and trichlorobenzene was flowed as an eluent at a flow rate of 1.0 ml / 10 minutes to obtain measured values of Mw and Mn.
- a calibration curve related to the molecular weight M was prepared using standard polystyrene manufactured by Tosoh Corporation, and the measured values were converted to polystyrene values to obtain Mw, Mn and Mz. Furthermore, the logarithm of the bottom 10 of the molecular weight M of standard polystyrene is referred to as logarithmic molecular weight (“Log (M)”).
- it is preferably 8.0% or more and 18.0% or less, more preferably 10.0% or more and 17.0% or less, and still more preferably Is 11.0 or more and 16.0 or less, and particularly preferably 12.0% or more and 16.0% or less.
- Such a differential distribution value can be obtained as follows using GPC.
- a curve (generally also referred to as “elution curve”) showing the intensity with respect to time obtained by a differential refraction (RI) detector of GPC is used.
- the elution curve is converted into a curve showing the intensity with respect to Log (M) by converting the time axis into logarithmic molecular weight (Log (M)). Since the RI detection intensity is proportional to the component concentration, an integral distribution curve with respect to the logarithmic molecular weight Log (M) can be obtained when the total area of the curve indicating the intensity is 100%.
- the differential distribution curve is obtained by differentiating the integral distribution curve with Log (M). Therefore, “differential distribution” means a differential distribution with respect to the molecular weight of the concentration fraction. From this curve, the differential distribution value at a specific Log (M) can be read to obtain the above relationship.
- the mesopentad fraction ([mmmm]) of polypropylene A is preferably 94.0% or more and less than 98.0%, more preferably 94.5% or more and 97.9% or less, and further preferably 94.5% or more and 97.97. It is 5% or less, particularly preferably 95.0% or more and 97.0% or less.
- the mesopentad fraction [mmmm] of polypropylene A is 94.0% or more and less than 98.0%, the crystallinity of the resin is moderately improved due to the reasonably high stereoregularity, the initial voltage resistance and the long-term There is a tendency that the withstand voltage over a moderately improved range.
- the speed of solidification (crystallization) at the time of forming the cast original fabric sheet is appropriate, and it can have appropriate stretchability.
- the mesopentad fraction ([mmmm]) is an index of stereoregularity that can be obtained by high temperature nuclear magnetic resonance (NMR) measurement.
- NMR nuclear magnetic resonance
- measurement can be performed using a high temperature Fourier transform nuclear magnetic resonance apparatus (high temperature FT-NMR), JNM-ECP500 manufactured by JEOL Ltd.
- the pentad fraction representing the degree of stereoregularity is a combination of the quintet (pentad) of the consensus “meso (m)” arranged in the same direction and the consensus “rasemo (r)” arranged in the opposite direction (mmmm and mrrm). Etc.) based on the integrated value of the intensity of each signal derived from.
- Each signal derived from mmmm, mrrm, etc. can be attributed with reference to, for example, “T. Hayashi et al., Polymer, 29, 138 (1988)”.
- polypropylene A has a weight average molecular weight (Mw) of 250,000 to 450,000; a molecular weight distribution (Mw / Mn) of 7.0 to 12.0; a Z average molecular weight / number average molecular weight (Mz / Mn). 20.0 or more and 70.0 or less;
- Mw weight average molecular weight
- Mw / Mn molecular weight distribution
- Mz / Mn Z average molecular weight / number average molecular weight
- the mesopentad fraction ([mmmm]) is preferably 94.0% or more and less than 98.0%.
- a logarithmic molecular weight Log (as a representative distribution value of components having a molecular weight of 10,000 to 100,000 on the low molecular weight side (hereinafter also referred to as “low molecular weight component”) from the Mw value (250,000 to 450,000).
- Polypropylene A preferably has a broad molecular weight distribution and at the same time contains a large amount of components having a molecular weight of 10,000 to 100,000 at a ratio of 8.0% or more and 18.0% or less as compared with a component having a molecular weight of 1,000,000. .
- the melt tension of polypropylene A at 230 ° C. is preferably 1 g or less.
- unstable flow such as melt fracture is unlikely to occur because of excellent flow characteristics in the melted state. Therefore, since the film thickness uniformity is good, there is an advantage that it is difficult to form a thin portion where dielectric breakdown is likely to occur.
- the melt tension was determined by using the Capillograph 1B manufactured by Toyo Seiki Co., Ltd., and the tension detected by the pulley when the resin was extruded in a string shape under the following conditions and wound on a roller was defined as the melt tension.
- the melt flow rate (MFR) of polypropylene A at 230 ° C. is preferably 1 to 10 g / 10 min, more preferably 1.5 to 8 g / 10 min, and particularly preferably 2 to 6 g / 10 min.
- MFR melt flow rate
- Polypropylene A can be produced using a generally known polymerization method. As long as the polypropylene A that can be used for the film of this embodiment can be produced, there is no particular limitation. Examples of such a polymerization method include a gas phase polymerization method, a bulk polymerization method, and a slurry polymerization method.
- Polymerization may be single-stage (one-stage) polymerization using one polymerization reactor, or multi-stage polymerization using at least two or more polymerization reactors. Furthermore, hydrogen or comonomer may be added to the reactor as a molecular weight regulator.
- the catalyst a generally known Ziegler-Natta catalyst or the like can be used, and there is no particular limitation as long as the polypropylene resin according to this embodiment can be obtained.
- the catalyst can also contain a promoter component and a donor.
- the molecular weight, molecular weight distribution, stereoregularity, and the like can be controlled by adjusting the catalyst and polymerization conditions.
- polypropylene A having a strain hardening parameter of less than 3 for example, by employing each polymerization method, a polypropylene having a branched structure with a short branched chain in the polypropylene molecule is obtained, or many branched structures in the polypropylene molecule are obtained. It is mentioned to obtain polypropylene that does not have (close to linear). In other words, the strain hardening parameter tends to increase when the branched chain in the polypropylene molecule is long when only the branched structure of the polymer is different and according to the MSF theory.
- polypropylene A having a strain hardening parameter of less than 3 can be obtained.
- the polymerization method and conditions such as temperature and pressure during the polymerization, (ii) the form of the reactor during the polymerization, (iii) the presence or absence of the additive, the type and The polypropylene A can be selectively obtained by appropriately selecting or adjusting the amount used, (iv) the type and amount of the polymerization catalyst, and the like.
- a slurry method using an inert solvent a bulk method using a monomer itself (eg, propylene) as a solvent without using an inert solvent, a solution polymerization method, and a monomer using substantially no liquid solvent.
- a gas phase method for keeping the gas in a gaseous state The reactor for the polymerization may be single-stage polymerization using one polymerization reactor, or may be multi-stage polymerization using two or more polymerization reactors.
- the polymerization catalyst a Ziegler-Natta catalyst or the like can be used, and the polymerization catalyst may contain a promoter component or a donor.
- the molecular weight, molecular weight distribution, stereoregularity, etc. of the polypropylene resin can be controlled by appropriately adjusting the polymerization catalyst and other polymerization conditions.
- the strain hardening parameter can be controlled by controlling the molecular weight, molecular weight distribution, stereoregularity, branching (amount, length, distribution) and the like of this polypropylene resin.
- the molecular weight distribution and the composition of the molecular weight can be easily adjusted by using a polymerization catalyst.
- Examples of the method obtained by the multistage polymerization reaction include the following methods.
- polymerization is performed at a high temperature in a plurality of reactors of a high molecular weight polymerization reactor and a low molecular weight or medium molecular weight reactor.
- the high molecular weight component and the low molecular weight component of the product resin are adjusted regardless of the order in the reactor.
- propylene and a catalyst are supplied to the first polymerization reactor.
- hydrogen as a molecular weight modifier is mixed in an amount necessary to reach the required polymer molecular weight.
- the reaction temperature is about 70 to 100 ° C.
- the residence time is about 20 to 100 minutes.
- Multiple reactors can be used, for example, in series, in which case the polymerization product of the first step is sent continuously to the next reactor along with additional propylene, catalyst, molecular weight modifier, followed by Thus, the second polymerization in which the molecular weight is adjusted to a low molecular weight or a high molecular weight in the first polymerization step is performed.
- the yield (production amount) of the first and second reactors By adjusting the yield (production amount) of the first and second reactors, the composition (configuration) of the high molecular weight component and the low molecular weight component can be adjusted.
- the catalyst may contain a promoter component and a donor.
- the molecular weight distribution can be controlled by appropriately adjusting the catalyst and polymerization conditions.
- composition of the molecular weight distribution of the polypropylene raw material resin is adjusted by peroxidative decomposition
- a method by peroxidation treatment with a decomposing agent such as hydrogen peroxide or organic oxide is preferable.
- a peroxide is added to a collapsible polymer such as polypropylene, a hydrogen abstraction reaction occurs from the polymer, and the resulting polymer radical partially recombines to cause a crosslinking reaction, but most radicals undergo secondary decomposition ( ⁇ cleavage). ) And is divided into two polymers having smaller molecular weights. Therefore, decomposition proceeds with a high probability from the high molecular weight component, so that the low molecular weight component increases and the structure of the molecular weight distribution can be adjusted.
- Examples of a method for obtaining a resin containing moderately low molecular weight components by peroxidative decomposition include the following methods.
- Polymerized polypropylene powder or pellets obtained by polymerization and, as an organic peroxide, for example, 1,3-bis- (tertiary-butyl peroxide isopropyl) -benzene and the like are 0.001% by mass to 0.5% by mass. %, Adjusting and adding in consideration of the composition (configuration) of the target high molecular weight component and low molecular weight component, and performing melt kneading at a temperature of about 180 ° C. to 300 ° C. in a melt kneader machine. You can also.
- the content of the low molecular weight component by blending it is preferable to dry mix or melt mix at least two types of resins having different molecular weights.
- a two-polypropylene mixed system in which the main resin is mixed with about 1 to 40% by mass of an additive resin having an average molecular weight higher or lower than that is preferable because the low molecular weight component amount can be easily adjusted. Used.
- melt flow rate (MFR) may be used as a measure of the average molecular weight.
- MFR melt flow rate
- the difference in MFR between the main resin and the additive resin is preferably about 1 to 30 g / 10 minutes from the viewpoint of convenience during adjustment.
- Examples of methods for adjusting “difference in differential distribution value” include methods for adjusting polymerization conditions, methods for adjusting molecular weight distribution, methods using a decomposing agent, and methods for selectively decomposing high molecular weight components.
- the method of mixing molecular weight resin is mentioned.
- the difference between the differential distribution values can be adjusted to a desired value by using these methods alone or in combination of two or more.
- polypropylene A a commercially available product (for example, polypropylene manufactured by Prime Polymer Co., Ltd.) can also be used.
- the content of polypropylene A in the film of the present embodiment is preferably 50% by mass or more and 99.9% by mass or less, more preferably 60% by mass or more and 99.5% by mass or less, and further preferably 70% by mass based on the resin component. It is 80% by mass or more and 98.5% by mass or less, and particularly preferably 90% by mass or more and 98% by mass or less.
- the film of this embodiment can contain 1 type, or 2 or more types of polypropylene A.
- the strain hardening parameter of polypropylene B is 3 or more and 20 or less. When the strain hardening parameter exceeds 20, excessive residual stress and anisotropy occur in the film, and problems such as impact resistance and stress crack resistance arise.
- the strain hardening parameter of polypropylene B is preferably 3.5 or more, more preferably 4 or more, still more preferably 5 or more, and particularly preferably 5.5 or more.
- a strain hardening parameter of 3 or more is preferable because the melt tension is hardly lowered by repeated kneading, and the strain hardening property of the resin during elongation deformation is maintained.
- the strain hardening parameter of polypropylene B is preferably 18 or less, more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. If the strain-hardening parameter of polypropylene B is 20 or less, it is preferable that the melt tension is hardly lowered by repeated kneading, and the strain-hardening property of the resin during elongation deformation is maintained.
- the strain hardening parameter tends to increase as the branched chain in the polypropylene molecule is long, as described in ⁇ Strain hardening parameter ( ⁇ )>. Therefore, polypropylene B can be obtained by adjusting the branched structure in the polypropylene molecule, the molecular chain length in the branched structure, and the like. Polypropylene B is preferably a long chain branched polypropylene. When the polypropylene B is a long-chain branched polypropylene, the strain hardening parameter becomes appropriate, which is preferable.
- Examples of the method for producing polypropylene B include a method of polymerizing propylene using a metallocene catalyst.
- the metallocene catalyst is generally a metallocene compound that forms a polymerization catalyst for producing an olefin macromer.
- polypropylene metallocene catalyst type polypropylene
- the branched chain length and the branched chain interval of the polypropylene become appropriate, and excellent compatibility with linear polypropylene and This is preferable because a uniform composition and surface shape can be obtained.
- polypropylene B In the production of polypropylene B, other conditions other than the type and amount of catalyst used, such as (i) polymerization conditions and conditions such as temperature and pressure during polymerization, (ii) reactor conditions during polymerization Form, (iii) Presence / absence of use, type and amount used, (iv) Methods for adjusting molecular weight, molecular weight distribution, and stereoregularity, (v) Methods for adjusting the difference in differential distribution values, etc. It may be the same as each condition described in the polypropylene A>.
- polymerization conditions and conditions such as temperature and pressure during polymerization, (ii) reactor conditions during polymerization Form, (iii) Presence / absence of use, type and amount used, (iv) Methods for adjusting molecular weight, molecular weight distribution, and stereoregularity, (v) Methods for adjusting the difference in differential distribution values, etc. It may be the same as each condition described in the polypropylene A>.
- a metallocene catalyst is used for the polymerization of polypropylene B, a long-chain branched polypropylene can be obtained without performing crosslinking and modification in the post-polymerization step. Since the biaxially stretched polypropylene film excellent by the strength of is obtained, it is preferable.
- the polypropylene obtained by polymerizing propylene using a metallocene catalyst is a method of forming a partial cross-linked structure by a method such as electron beam irradiation in the post-polymerization step of the resin, a cross-linking aid and a peroxide.
- a method such as electron beam irradiation in the post-polymerization step of the resin, a cross-linking aid and a peroxide.
- the gel fraction of polypropylene B is preferably 1000 ppm by mass or less, more preferably 800 ppm by mass or less, still more preferably 500% by mass with respect to the mass of polypropylene B in the resin component (by mass when polypropylene B is used as a whole).
- the mass ppm or less particularly preferably 100 mass ppm or less.
- the gel fraction of polypropylene B is 1000 mass ppm or less, insulation defects are reduced, and a biaxially stretched polypropylene film excellent in dielectric breakdown strength is obtained, which is preferable.
- the smaller the gel fraction of polypropylene B the better. Therefore, although the lower limit is not particularly limited, it is, for example, 0 mass ppm, 1 mass ppm, 10 mass ppm, 250 mass ppm or the like.
- the gel fraction of polypropylene B can be measured as described above.
- the weight average molecular weight (Mw) of polypropylene B is preferably 150,000 to 600,000, more preferably 200,000 to 500,000, further preferably 250,000 to 450,000, and particularly preferably 260,000 to 420,000. is there.
- Mw weight average molecular weight
- the resin fluidity is appropriate, the thickness of the cast raw sheet is easy to control, and it is easy to produce a thin stretched film Can be. Furthermore, it becomes difficult to generate unevenness in the thickness of the sheet and film, and the sheet can have appropriate stretchability, which is preferable.
- the molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn)) of polypropylene B is preferably 1.5 or more and 4.5 or less, more preferably 1.8 or more and 4.2 or less, and still more preferably 2.0. It is 4.0 or less, particularly preferably 2.1 or more and 3.9 or less, and particularly preferably 2.2 or more and 3.8 or less.
- the molecular weight distribution (Z average molecular weight / number average molecular weight (Mz / Mn)) of polypropylene B is preferably 4.0 or more and 9.0 or less, more preferably 4.2 or more and 8.8 or less, and still more preferably 4 0.5 or more and 8.5 or less, particularly preferably 5.0 or more and 8.2 or less.
- the weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight (Mz) and molecular weight distribution (Mw / Mn and Mz / Mn) of polypropylene B were measured using a gel permeation chromatograph (GPC) apparatus. can do. More specifically, for example, it can be measured by a high temperature GPC-MALS measurement, that is, a high temperature GPC apparatus (HLC-8121GPC / HT; manufactured by Tosoh Corporation) equipped with a light scattering detector (DAWN EOS; manufactured by Wyatt Technology).
- GPC gel permeation chromatograph
- TSKgel guardcolumnHHR (30) (7.8 mmID ⁇ 7.5 cm), manufactured by Tosoh Corporation, and three TSKgel GMH-HR-H (20) HT (7.8 mmID ⁇ 30 cm) were connected. Used. The column temperature was set to 140 ° C., and trichlorobenzene was flowed as an eluent at a flow rate of 1.0 ml / min to obtain measured values of Mw and Mn.
- the molecular weight and molecular weight distribution of polypropylene B can be controlled by adjusting the catalyst and polymerization conditions.
- the melt tension of polypropylene B at 230 ° C. is preferably 1 to 50 g, more preferably 2 to 40 g, and even more preferably 4 to 30 g.
- the melt tension of polypropylene B at 230 ° C. is within the above range, unstable flow such as melt fracture is unlikely to occur because of excellent flow characteristics in the melted state. Therefore, since the film thickness uniformity is good, there is an advantage that it is difficult to form a thin portion where dielectric breakdown is likely to occur.
- the melt flow rate (MFR) of polypropylene B at 230 ° C. is preferably 0.1 to 12 g / 10 min, more preferably 0.5 to 11 g / 10 min, and further preferably 1 to 10 g / 10 min.
- MFR melt flow rate
- the content of polypropylene B in the film of this embodiment is preferably 0.1% by mass or more and 50% by mass, more preferably 0.5% by mass or more and 40% by mass or less, more preferably 1.% by mass based on the resin component. 5 mass% or more and 30 mass% or less, Especially preferably, they are 3 mass% or more and 20 mass% or less, More preferably, they are 3.5 mass% or more and 10 mass% or less.
- the film of this embodiment can contain 1 type, or 2 or more types of polypropylene B.
- Examples of typical commercial products of polypropylene B include MFX3 and MFX6 manufactured by Nippon Polypro Co., Ltd., MFX8 manufactured by Nippon Polypro Co., Ltd. and the like.
- the total mass% of polypropylene A and polypropylene B with respect to the entire resin component constituting the film of the present embodiment is preferably 90 mass% or more, more preferably 95 mass% or more, still more preferably 99 mass% or more, particularly preferably 100. It is mass% (that is, the resin component which comprises the film of this embodiment is two types, polypropylene A and polypropylene B).
- resin components (other resin components) other than polypropylene A and polypropylene B include olefin resins that do not correspond to either polypropylene A or polypropylene B.
- the film of the present embodiment may further contain at least one additive in addition to the resin component.
- the “additive” is generally an additive used for polypropylene, and is not particularly limited as long as the biaxially stretched polypropylene film intended by the present invention can be obtained.
- Additives include, for example, ⁇ crystal nucleating agents, antioxidants, necessary stabilizers such as chlorine absorbers and ultraviolet absorbers, lubricants, plasticizers, flame retardants, antistatic agents and the like.
- the film of this embodiment can contain the additive in an amount that does not adversely affect the biaxially stretched polypropylene film targeted by the present invention.
- the “ ⁇ crystal nucleating agent” is generally used for polypropylene and is not particularly limited as long as the biaxially stretched polypropylene film targeted by the present invention can be obtained.
- the ⁇ crystal nucleating agent can be used after being dry blended or melt blended with a polypropylene raw material and pelletized, or can be used together with polypropylene pellets in an extruder. By using a ⁇ crystal nucleating agent, the surface roughness of the film can be adjusted to a desired roughness.
- An example of a typical commercial product of a ⁇ crystal nucleating agent is NJ Star NU-100 manufactured by Shin Nippon Rika Co., Ltd.
- the content thereof is preferably 1 to 1000 ppm by mass, more preferably relative to the mass of the resin component (by mass when the resin component as a whole). 50 to 600 ppm by mass.
- the “antioxidant” is generally called an antioxidant and is not particularly limited as long as it can be used for polypropylene and a biaxially stretched polypropylene film intended by the present invention can be obtained.
- Antioxidants are generally used for two purposes. One purpose is to suppress thermal deterioration and oxidation deterioration in the extruder, and the other purpose is to contribute to suppression of deterioration and improvement of capacitor performance in long-term use as a capacitor film.
- An antioxidant that suppresses thermal degradation and oxidative degradation in the extruder is also referred to as a “primary agent”, and an antioxidant that contributes to improving capacitor performance is also referred to as a “secondary agent”.
- antioxidants Two types of antioxidants may be used for these two purposes, or one type of antioxidant may be used for the two purposes.
- the primary agent examples include 2,6-ditertiary-butyl-para-cresol (generic name: BHT).
- BHT 2,6-ditertiary-butyl-para-cresol
- the primary agent is usually added for the purpose of suppressing thermal deterioration and oxidative deterioration in the extruder during the preparation of the polypropylene resin composition described in ⁇ Method for producing film of this embodiment> described later. it can.
- most of the antioxidant added to the polypropylene resin composition is consumed in the molding process in the extruder, and hardly remains in the film after film formation. Therefore, when the film of this embodiment contains a primary agent, the content is usually less than 100 ppm by mass with respect to the mass of the resin component (by mass when the resin component is used as a whole).
- Examples of the secondary agent include hindered phenol antioxidants having a carbonyl group.
- the “hindered phenol-based antioxidant having a carbonyl group” is usually a hindered phenol-based antioxidant having a carbonyl group, and particularly as long as the biaxially stretched polypropylene film intended by the present invention can be obtained. There is no limit.
- hindered phenol-based antioxidant having a carbonyl group for example, triethylene glycol-bis [3- (3-tertiary-butyl-5-methyl-4-hydroxyphenyl) propionate] (trade name: Irganox 245) ), 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 259), pentaerythritol tetrakis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010), 2,2-thio-diethylenebis [3- (3,5-di-tertiary-butyl-4- Hydroxyphenyl) propionate] (trade name: Irganox 1035), Octade 3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate (trade name: I
- the film of the present embodiment may contain one or more hindered phenol antioxidants (secondary agents) having a carbonyl group for the purpose of suppressing deterioration that progresses with time during long-term use.
- the content is based on the mass of the resin component (by mass when the resin component is the whole), Preferably it is 4000 mass ppm or more and 6000 mass ppm or less, More preferably, it is 4500 mass ppm or more and 6000 mass ppm or less.
- the content of the hindered phenol-based antioxidant having a carbonyl group in the film is preferably 4000 ppm by mass or more and 6000 ppm by mass or less from the viewpoint of appropriate effects.
- the capacitor film including the film of this embodiment containing a hindered phenol-based antioxidant having a carbonyl group that has good compatibility with polypropylene at a molecular level and containing an amount in an optimal specific range has long-term durability. Since it improves, it is preferable.
- the “chlorine absorbent” is generally called a chlorine absorbent and is not particularly limited as long as it can be used for polypropylene and a biaxially stretched polypropylene film intended by the present invention can be obtained.
- the chlorine absorbent include metal soaps such as calcium stearate.
- the film of this embodiment can contain the chlorine absorbent in an amount that does not adversely affect the biaxially oriented polypropylene film targeted by the present invention.
- the thickness of the film of the present embodiment is preferably 0.8 ⁇ m or more and 50 ⁇ m or less, more preferably 1.0 ⁇ m or more and 30 ⁇ m or less, further preferably 1.5 ⁇ m or more and 20 ⁇ m or less, and particularly preferably 1. They are 7 micrometers or more and 10 micrometers or less, More preferably, they are 1.8 micrometers or more and 7 micrometers or less. Moreover, it is also preferable that the thickness of the film of this embodiment is larger than 15 micrometers and less than 50 micrometers. The thickness of the film of this embodiment is more preferably greater than 16 ⁇ m and less than 30 ⁇ m, and even more preferably greater than 17 ⁇ m and less than 20 ⁇ m. The film of this embodiment is preferably a very thin film.
- the thickness of the film of the present invention refers to a value measured according to JIS-C2330 using a micrometer (JIS-B7502).
- the AC breakdown strength (ES) of the film of this embodiment is preferably 240 [V AC / ⁇ m] or more, more preferably 243 [V AC / ⁇ m] or more, and further preferably 245 [V AC / ⁇ m]. That's it.
- the DC breakdown strength (ES) of the film of the present embodiment is preferably 465 [V DC / ⁇ m] or more, more preferably 470 [V DC / ⁇ m] or more, and further preferably 480 [V DC / ⁇ m]. ⁇ m] or more.
- the DC breakdown strength (ES) of the biaxially stretched film can be measured according to JIS C 2330: 2010 and JIS C 2151: 2006 17.2.2 (dielectric breakdown voltage / plate electrode method).
- a withstand voltage tester can be used for the measurement.
- the melting point in the first run of the film of this embodiment is preferably 166 ° C. or higher, more preferably 168 ° C. or higher, and further preferably 169 ° C. or higher.
- the melting point in the first run is preferably 188 ° C. or lower, more preferably 187 ° C. or lower, and further preferably 185 ° C. or lower.
- the upper limit of the melting point in the first run is not more than the equilibrium melting point of polypropylene (melting point when the thickness of the lamella is infinite), and is preferably 187 ° C. or less from the viewpoint of moldability.
- the melting point in the first run is a value obtained by a first run of differential scanning calorimetry, and specifically, a value measured by the method described in the examples.
- the enthalpy of fusion in the first run of the film of this embodiment is preferably 105 J / g or more, more preferably 106 J / g or more, and even more preferably 107 J / g or more.
- the melting enthalpy in the first run is 105 J / g or more, the crystallinity required for maintaining the strength of dielectric breakdown is obtained.
- the enthalpy of melting in the first run is preferably 150 J / g or less, more preferably 130 J / g or less, and still more preferably 120 J / g or less.
- the melting enthalpy in the first run is 150 J / g or less, suitable thin film stretchability is obtained.
- the melting enthalpy in the first run is a value obtained by the first run of differential scanning calorimetry, and specifically, a value measured by the method described in the examples.
- the crystallization temperature in the first run of the film of the present embodiment is preferably 112.8 ° C. or higher, more preferably 112.9 ° C. or higher, and further preferably 113 ° C. or higher.
- the crystallization temperature in the first run is preferably 125 ° C. or lower, more preferably 123 ° C. or lower, and still more preferably 122 ° C. or lower.
- the crystallization temperature in the first run is 125 ° C. or lower, it is possible to form a rough surface by crystal transformation.
- the crystallization temperature in the first run is a value obtained by the first run of differential scanning calorimetry, and specifically, a value measured by the method described in the examples.
- the crystallization enthalpy in the first run of the film of the present embodiment is preferably ⁇ 150 J / g or more, more preferably ⁇ 130 J / g or more, further preferably ⁇ 120 J / g or more, particularly preferably ⁇ 110 J / g or more. is there.
- the crystallization enthalpy in the first run is preferably ⁇ 98 J / g or less, more preferably ⁇ 100 J / g or less, and further preferably ⁇ 102 J / g or less.
- the crystallization enthalpy in the first run is ⁇ 98 J / g or less, the crystallinity necessary for maintaining the strength of dielectric breakdown is obtained.
- the crystallization enthalpy in the first run is a value obtained by the first run of differential scanning calorimetry, and specifically, a value measured by the method described in the examples.
- the melting point in the second run of the film of this embodiment is preferably 160 ° C. or higher, more preferably 161 ° C. or higher, and still more preferably 162 ° C. or higher.
- the melting point in the second run is 160 ° C. or more, it is easy to obtain a film having a lamella thickness necessary for maintaining the strength of dielectric breakdown.
- the melting point in the second run is preferably 188 ° C. or lower, more preferably 170 ° C. or lower, and further preferably 165 ° C. or lower.
- the melting point in the second run is preferably 188 ° C. or less from the viewpoint of moldability.
- the melting point of the second run is a value determined by the second run of differential scanning calorimetry, and specifically, a value measured by the method described in the examples.
- the melting enthalpy in the second run of the film of this embodiment is preferably 95 J / g or more, more preferably 97 J / g or more, and still more preferably 98 J / g or more.
- the melting enthalpy in the second run is preferably 110 J / g or less, more preferably 105 J / g or less, and still more preferably 103 J / g or less.
- the melting enthalpy in the second run is a value obtained by the second run of differential scanning calorimetry, and specifically, a value measured by the method described in the examples.
- the biaxially stretched polypropylene film of this embodiment is a generally known method for producing a biaxially stretched polypropylene film, for example, polypropylene A and polypropylene B, if necessary, mixed with other resins and / or additives. It can manufacture by producing a cast original fabric sheet from the polypropylene resin composition obtained by doing, and then biaxially stretching the cast original fabric sheet.
- the method for preparing the polypropylene resin composition is not particularly limited, but the polymer powder or pellets of polypropylene A and polypropylene B can be dried together with other resins and / or additives as necessary using a mixer or the like.
- the mixer or kneader may be either a single screw type, a biaxial screw type, or a multi-screw type having more than that. Furthermore, in the case of a screw type having two or more axes, either a kneading type rotating in the same direction or rotating in a different direction may be used.
- the kneading temperature is not particularly limited as long as good kneading is obtained, but it is preferably in the range of 170 to 320 ° C, more preferably in the range of 200 ° C to 300 ° C, and still more preferably. Is 230 ° C. to 270 ° C.
- a too high kneading temperature is not preferable because it causes deterioration of the resin.
- the kneader may be purged with an inert gas such as nitrogen.
- the melt-kneaded resin is pelletized to an appropriate size using a generally known granulator, whereby pellets of the melt blend resin composition can be obtained.
- the primary agent as the antioxidant described in the above ⁇ Additive> can be added for the purpose of suppressing thermal deterioration and oxidative deterioration in the extruder.
- the content thereof is preferably 1000 mass ppm to 5000 mass ppm with respect to the mass of the resin component (by mass when the resin component as a whole). Most of the antioxidant for this purpose is consumed in the molding process in the extruder, and hardly remains in the film after film formation.
- the hindered phenol-based antioxidant having a carbonyl group described in the above ⁇ Additive> can be added to the polypropylene resin composition as a secondary agent.
- the content thereof is preferably 100 mass ppm to the mass of the resin component (by mass when the resin component as a whole). It is 10,000 mass ppm, more preferably 5500 mass ppm to 7000 mass ppm. Not only in the extruder, but also hindered phenolic antioxidants having carbonyl groups are consumed.
- a polypropylene resin composition does not contain a primary agent, more hindered phenolic antioxidants having a carbonyl group can be used.
- the amount of hindered phenol antioxidant having a carbonyl group increases in the extruder.
- the content is based on the mass of the resin component (in terms of the mass of the resin component as a whole). ) 6000 mass ppm to 8000 mass ppm or less.
- the total ash due to the polymerization catalyst residue contained in the polypropylene resin composition is as small as possible in order to improve the electrical characteristics.
- the total ash content is preferably 50 mass ppm or less, more preferably 40 mass ppm or less, and even more preferably 30 mass ppm or less with respect to the mass of the resin component (by mass when the resin component is the whole).
- the cast raw fabric sheet is prepared by supplying pellets of a dry blend resin composition and / or a melt blend resin composition prepared in advance to an extruder, heating and melting, and passing through a filtration filter, and preferably 170 ° C. to 320 ° C. , More preferably 200 ° C. to 300 ° C. and melt extrusion from a T die, preferably 40 ° C. to 140 ° C., more preferably 80 ° C. to 140 ° C., further preferably 90 ° C. to 140 ° C., particularly preferably 90 ° C. It can be obtained by cooling and solidifying at least one metal drum maintained at a temperature (cast temperature) of ⁇ 120 ° C., more preferably 90-105 ° C.
- the thickness of the cast raw sheet is not particularly limited as long as the biaxially stretched polypropylene film targeted by the present invention can be obtained, but is preferably 0.05 mm to 2 mm, more preferably 0.1 mm. ⁇ 1 mm.
- the polypropylene undergoes thermal degradation (oxidation degradation) and shear degradation.
- the degree of progress of such deterioration depends on the nitrogen purge in the extruder (suppression of oxidation), the screw shape (shearing force) in the extruder, and the internal shape of the T-die during casting ( It can be suppressed by the shearing force), the amount of antioxidant added (suppression of oxidation), the winding speed (elongation force) during casting, and the like.
- the film of this embodiment can be manufactured by performing an extending
- a sequential biaxial stretching method is preferred.
- the sequential biaxial stretching method first, the cast raw sheet is preferably maintained at a temperature of 100 to 180 ° C., more preferably 140 to 160 ° C., and it is passed 3 to 7 times in the flow direction through a roll having a speed difference. And immediately cool to room temperature.
- the temperature in the longitudinal stretching step the ⁇ crystal melts and transitions to the ⁇ crystal, and the unevenness becomes obvious.
- the stretched film is guided to a tenter, and is stretched 3 to 11 times in the width direction at a temperature of preferably 160 ° C. or more, more preferably 160 to 180 ° C., and then subjected to relaxation and heat setting and winding.
- the wound film can be cut to a desired product width after aging treatment in an atmosphere of about 20 to 45 ° C.
- the film has excellent mechanical strength and rigidity, and the surface irregularities are further clarified, resulting in a finely roughened biaxially stretched film.
- the biaxially stretched polypropylene film of the present embodiment may be subjected to corona discharge treatment online or offline after the stretching and heat setting process for the purpose of improving adhesive properties in the subsequent process such as a metal deposition process.
- the corona discharge treatment can be performed using a known method. It is preferable to use air, carbon dioxide gas, nitrogen gas, and a mixed gas thereof as the atmospheric gas.
- this embodiment is a metallized film having a metal film on at least one surface of a polypropylene film.
- Examples of the method for metallizing the film surface of the present embodiment include, but are not limited to, a vacuum deposition method and a sputtering method. From the viewpoint of productivity and economy, the vacuum deposition method is preferable.
- Examples of the vacuum deposition method generally include a crucible method and a wire method, but are not particularly limited, and an optimum one can be selected as appropriate.
- the metal used for example, simple metals such as zinc, lead, silver, chromium, aluminum, copper, and nickel, a mixture of plural kinds thereof, and alloys thereof can be used. In consideration of capacitor performance and the like, at least one selected from the group consisting of zinc and aluminum is preferable.
- a metal film obtained by vapor deposition is also referred to as a metal vapor deposition film.
- the film resistance value of the metal film is preferably 1 to 100 ⁇ / ⁇ from the viewpoint of the electrical characteristics of the capacitor. A higher value within this range is desirable from the viewpoint of self-healing (self-healing) characteristics, and the film resistance is preferably 5 ⁇ / ⁇ or more, more preferably 10 ⁇ / ⁇ or more. From the viewpoint of safety as a capacitor element, the membrane resistance is preferably 50 ⁇ / ⁇ or less, more preferably 20 ⁇ / ⁇ or less.
- the film resistance value of the metal film can be measured in the metal film by, for example, a two-terminal method known to those skilled in the art.
- the film resistance value of the metal film can be adjusted, for example, by adjusting the evaporation amount by adjusting the output of the evaporation source.
- the thickness of the metal film is not particularly limited, but is preferably 1 nm to 100 nm.
- an insulating margin is formed without depositing a certain width from one end of the film so that a capacitor is formed when the film is wound.
- the film resistance of the heavy edge is preferably 2 to 8 ⁇ / ⁇ . More preferably, it is 3 to 6 ⁇ / ⁇ .
- the margin pattern for metallization by vapor deposition is not particularly limited, but a pattern including a so-called special margin such as a fish net pattern or a T margin pattern is used in order to improve characteristics such as the safety of the capacitor.
- a so-called special margin such as a fish net pattern or a T margin pattern
- the safety is improved, and it is effective and preferable from the viewpoint of destruction of the capacitor and prevention of short circuit.
- a generally known method such as a tape method or an oil method can be used without any limitation.
- the film of the present embodiment to which an electrode is attached or metallized is wound alone or in combination of two or more, preferably in combination of two.
- the number of windings can be appropriately selected according to the use of the capacitor.
- Winding can be performed using an automatic winder.
- the element wound element can be heat-treated under pressure and / or heating.
- the pressure under the above pressure is, for example, about 200 to 1000 kPa.
- the temperature under the heating is, for example, about 60 to 130 ° C.
- zinc metal is sprayed onto the heat-treated element end face. Thereby, a flat capacitor can be obtained.
- the metallized film of the present embodiment has excellent dielectric breakdown strength, it is suitable as a dielectric film for capacitors such as high voltage capacitors, various switching power supplies, filter capacitors such as converters and inverters, and smoothing capacitors. Can be used. Moreover, you may use for the inverter power supply circuit smoothing capacitor which controls the drive motor used for an electric vehicle, a hybrid vehicle, etc.
- the electrode can be used as a capacitor by attaching electrodes to the film of this embodiment.
- the method for attaching the electrode is not particularly limited, and generally known methods can be used. Moreover, it does not specifically limit as an electrode, The electrode normally used in order to manufacture a capacitor
- the present embodiment is a capacitor including a metallized film having a metal film on at least one side of the polypropylene film of the present embodiment.
- the film of this embodiment can be used very suitably for a capacitor because of its high dielectric breakdown strength.
- the capacitance of the capacitor is preferably 5 ⁇ F or more, more preferably 10 ⁇ F or more, and further preferably 20 ⁇ F or more.
- Polypropylene resin The polypropylene resins used to produce the polypropylene films of the examples and comparative examples are shown in Table 1 below. Unless otherwise specified, the terms “parts” and “%” indicate “parts by mass” and “% by mass”, respectively.
- Polypropylene resin A has the number average molecular weight (Mn), weight average molecular weight (Mw), z average molecular weight (Mz), molecular weight distribution (Mw / Mn), and molecular weight distribution (Mz / Mn) shown in Table 1 below.
- Resin A1 isotactic polypropylene, manufactured by Prime Polymer Co., Ltd .; hereinafter referred to as Resin A1 was used. These values are values measured in accordance with the above measurement method in the form of raw material resin pellets.
- the polypropylene resin B has the following number average molecular weight (Mn), weight average molecular weight (Mw), z average molecular weight (Mz), molecular weight distribution (Mw / Mn), and molecular weight distribution (Mz / Mn) shown in Table 1 below. Each polypropylene was used.
- Polypropylene B1 (Nippon Polypro Corporation WAYMAX MFX6, long-chain branched polypropylene obtained by polymerizing propylene using a metallocene catalyst; hereinafter referred to as resin B1)
- Polypropylene B2 (Nippon Polypro Corporation WAYMAX MFX8, a long-chain branched polypropylene obtained by polymerizing propylene using a metallocene catalyst; hereinafter referred to as resin B2)
- Polypropylene B3 (Nippon Polypro Corporation WAYMAX MFX3, long-chain branched polypropylene obtained by polymerizing propylene using a metallocene catalyst; hereinafter referred to as resin B3) was used.
- polypropylene resin B ′ As polypropylene resin B ′, B′4 (Daploy WB135HMS manufactured by Borealis AG, long-chain branched polypropylene obtained by cross-linking modification with peroxide; hereinafter referred to as resin B′4), was used.
- Table 1 shows the strain hardening parameters, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and molecular weight distribution (Mz / Mn) of the polypropylene resins A1 and B1 to B′4.
- ⁇ Strain hardening parameter> a) Dynamic viscoelasticity measuring apparatus: ARES-G2 (manufactured by TA Instruments) Jig: Cone plate (25 mm ⁇ , 0.1 rad.) Temperature: 230 ° C Frequency: 100 to 0.01 rad. / Sec. b) Elongation Viscosity Measurement Device: ARES-G2 (manufactured by TA Instruments) Jig: Elongation viscosity fixture temperature: 230 ° C Strain rate: 0.1 / s. However, when the torque was low under these conditions and the extensional viscosity could not be measured, the strain rate was set to 1.0 / s.
- Preliminary strain 0.2 mm Measurement procedure: (1) The resin pellets were heated and compressed at 230 ° C. for 5 minutes using a hot press machine to produce a press sheet of about 0.6 mm. The obtained press sheet was subjected to shear viscoelasticity measurement (frequency dispersion) and elongational viscosity measurement using a rheometer ARES-G2 manufactured by TA Instruments. (2) For shear viscoelasticity measurement (frequency dispersion), a press sheet was sandwiched between cone plate jigs (25 mm ⁇ , 0.1 rad), and measurement was performed at 230 ° C. with a frequency of 100 to 0.01 rad / sec. (3) The extensional viscosity was measured at 230 ° C.
- the extension viscosity measuring jig is a jig for measuring the extension viscosity of a high viscosity substance such as a molten polymer, and is composed of a fixed part and a rotating drum so that it can be pulled at a constant Henky strain rate. Yes. (4) Based on the method described in “Kunihiro Ozaki, Nobuo Murai, Nobuo Bessho Kinetsu, Journal of Japanese Society of Rheology Vol.
- ⁇ Gel fraction> The measurement conditions for the gel fraction of each resin were as follows. Sample amount: about 1g Solvent: Xylene (200 mL) Heating temperature: 120 ° C Heating time: 12 hours Filtration mesh: 200 mesh wire mesh drying: Room temperature ⁇ 8 hours + 80 ° C. ⁇ 3 hr About 1 g of a weighed sample was put into 200 mL of xylene and heated at 120 ° C. for 12 hours. The obtained liquid was filtered through a weighed 200 mesh wire net. The filtered mesh was dried at room temperature for 8 hours and at 80 ° C. for 3 hours. The filtered mesh was weighed, and the ratio of the residue was taken as the gel fraction.
- HLC-8121GPC-HT type which is a high temperature GPC device with a built-in differential refractometer (RI), manufactured by Tosoh Corporation was used.
- RI differential refractometer
- the number average molecular weight (Mn), the weight average molecular weight (Mw) and the z average molecular weight (Mz) were obtained.
- the molecular weight distribution (Mz / Mn) was obtained using the values of Mz and Mn, and the molecular weight distribution (Mw / Mn) was obtained using the values of Mw and Mn.
- the measurement conditions are as follows.
- GPC device HLC-8121GPC / HT (manufactured by Tosoh Corporation)
- Light scattering detector DAWN EOS (Wyatt Technology)
- Eluent 0.05 wt% BHT in 1,2,4-trichlorobenzene Flow rate: 1.0 mL / min Sample concentration: 2 mg / mL Injection volume: 300 ⁇ L
- System temperature 40 ° C
- Pretreatment The sample was precisely weighed, the eluent was added and dissolved by shaking at 140 ° C. for 1 hour, and hot filtration was performed with a 0.5 ⁇ m sintered metal filter.
- Measuring instrument manufactured by JEOL Ltd., high temperature FT-NMR JNM-ECP500 Observation nucleus: 13 C (125 MHz) Measurement temperature: 135 ° C
- Solvent Ortho-dichlorobenzene [ODCB: Mixed solvent of ODCB and deuterated ODCB (4/1)]
- melt tension the tension detected by the pulley when the resin was extruded in a string shape under the following conditions and wound on a roller was defined as the melt tension.
- Capillary 2.0mm diameter, 40mm length Cylinder diameter: 9.55mm Cylinder extrusion speed: 20 mm / min Winding speed: 4.0 m / min Temperature: 230 ° C.
- the melt tension is extremely high, the resin may break at a take-up speed of 4.0 m / min. In such a case, the take-up speed is lowered and the tension at the highest take-up speed is increased. Use melt tension.
- polypropylene films of Examples 1 to 6 and Comparative Examples 1 to 6 were produced, and their physical properties were evaluated.
- Example 2 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the resin B2 was used instead of the resin B1.
- the thickness of the obtained biaxially stretched polypropylene film was 18 ⁇ m.
- the compounding ratio of the resin and the physical property values of the obtained film are summarized in Table 2.
- Example 3 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the resin A1 and the resin B1 were used in the mass ratio shown in Table 1. The thickness of the obtained biaxially stretched polypropylene film was 18 ⁇ m. The compounding ratio of the resin and the physical property values of the obtained film are summarized in Table 2.
- Example 4 A biaxially stretched polypropylene film was obtained in the same manner as in Example 3 except that the resin B2 was used instead of the resin B1.
- the thickness of the obtained biaxially stretched polypropylene film was 18 ⁇ m.
- the compounding ratio of the resin and the physical property values of the obtained film are summarized in Table 2.
- Example 5 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the resin B3 was used instead of the resin B1.
- the thickness of the obtained biaxially stretched polypropylene film was 18 ⁇ m.
- the compounding ratio of the resin and the physical property values of the obtained film are summarized in Table 2.
- the stretched film was guided to a tenter and stretched 10 times in the width direction at a lateral stretching temperature of 158 ° C., and then relaxed and heat-set, and a biaxially stretched polypropylene film having a thickness of 2.5 ⁇ m was wound up.
- Example 1 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that only the resin A1 was used alone as the resin component. The thickness of the obtained biaxially stretched polypropylene film was 18 ⁇ m. The compounding ratio of the resin and the physical property values of the obtained film are summarized in Table 2.
- Example 2 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the resin B′4 was used instead of the resin B1. The thickness of the obtained biaxially stretched polypropylene film was 18 ⁇ m. The compounding ratio of the resin and the physical property values of the obtained film are summarized in Table 2.
- Example 3 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that only the resin B1 was used as the resin component, but a smooth cast sheet could not be produced due to melt fracture during extrusion molding. . Therefore, when the obtained cast sheet was stretched, breakage occurred and a stretched film could not be obtained.
- Example 4 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that only the resin B2 was used alone as the resin component, and a smooth cast sheet could not be produced due to melt fracture during extrusion molding. . Therefore, when the obtained cast sheet was stretched, breakage occurred and a stretched film could not be obtained.
- Example 5 A biaxially stretched polypropylene film was obtained in the same manner as in Example 6 except that only the resin A1 was used instead of the dry blend of the resin A1 and the resin B1. The thickness of the obtained biaxially stretched polypropylene film was 2.5 ⁇ m. The compounding ratio of the resin and the physical property values of the obtained film are summarized in Table 2.
- Example 6 Comparative Example 5 and Comparative Example 6, DC breakdown was measured.
- the strength (ES) of was measured.
- the load is higher when the voltage is applied with alternating current than when the voltage is applied with direct current.
- Examples 1 to 5 and Comparative Examples 1 and 2 having a thickness of 18 ⁇ m were measured with alternating current because the load was not sufficient when measured with direct current and appropriate evaluation could not be performed.
- Example 6, Comparative Example 5, and Comparative Example 6 having a thickness of 2.5 ⁇ m a sufficient load can be applied by direct current, and therefore measurement was performed by direct current.
- a T margin vapor deposition pattern was applied by aluminum vapor deposition with a vapor deposition resistance of 12 ⁇ / ⁇ to form a metal film to obtain a metallized film.
- the two metallized films were combined, and 1360 turns were wound at a winding tension of 200 g using an automatic winder 3KAW-N2 manufactured by Minato Seisakusho.
- the element wound element was heat treated at 120 ° C. for 4 hours while pressing, and then zinc metal was sprayed on the element end face to obtain a flat capacitor.
- the capacitance of the completed capacitor was 100 ⁇ F ( ⁇ 5 ⁇ F).
- the film of the present invention has a high dielectric breakdown strength and is extremely suitable as a capacitor film.
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Abstract
Description
[1] 歪み硬化性パラメータが3未満であるポリプロピレンAと、
歪み硬化性パラメータが3以上20以下であるポリプロピレンBと
を樹脂成分として含有することを特徴とする、二軸延伸ポリプロピレンフィルム。
[2] 前記ポリプロピレンBは長鎖分岐ポリプロピレンである、[1]に記載の二軸延伸ポリプロピレンフィルム。
[3] 前記ポリプロピレンBのゲル分率は前記ポリプロピレンBの質量を基準に1000質量ppm以下である、[1]または[2]に記載の二軸延伸ポリプロピレンフィルム。
なお、「前記ポリプロピレンBのゲル分率は前記ポリプロピレンBの質量を基準に1000質量ppm以下である」とは、「前記ポリプロピレンBのゲル分率は前記ポリプロピレンBを全体としたときに質量で1000質量ppm以下である」ことを意味する。
[4] 前記ポリプロピレンBは、メタロセン触媒を用いてプロピレンを重合することにより得られたものである、[1]~[3]のいずれかに記載の二軸延伸ポリプロピレンフィルム。
[5] 前記ポリプロピレンBの分子量分布(Mw/Mn)は1.5以上4.5以下である、[1]~[4]のいずれかに記載の二軸延伸ポリプロピレンフィルム。
[6] 前記ポリプロピレンAとポリプロピレンBの質量比率は、ポリプロピレンA:ポリプロピレンB=50:50~99.9:0.1である、[1]~[5]のいずれかに記載の二軸延伸ポリプロピレンフィルム。
[7] 前記ポリプロピレンAの分子量分布(Mw/Mn)は7.0以上12.0以下である、[1]~[6]のいずれかに記載の二軸延伸ポリプロピレンフィルム。
[8] コンデンサ用である、[1]~[7]のいずれかに記載の二軸延伸ポリプロピレンフィルム。
[9] [1]~[8]のいずれかに記載のポリプロピレンフィルムの少なくとも片面に金属膜を有する金属化フィルム。
[10] [9]に記載の金属化フィルムを含むコンデンサ。
以下、本発明の一実施形態に係る二軸延伸ポリプロピレンフィルムについて説明する。
本実施形態に係るフィルムは、歪み硬化性パラメータが3未満であるポリプロピレンAと、歪み硬化性パラメータが3以上20以下であるポリプロピレンBとを樹脂成分として含有することを特徴とする二軸延伸ポリプロピレンフィルムである。
歪み硬化性パラメータ(λ)は以下の通り求める。樹脂ペレットからプレスシートを得て、そのプレスシートを用いて剪断粘弾性および伸長粘度の測定を行う。剪断粘弾性測定から粘度成長関数
を求め、伸長粘度測定から非定常一軸伸長粘度関数ηE(t)を求め、ηE(t)において歪の大きさが2以上で伸長粘度が最大となる点における時間をtmaxとして、下記の(A)式:
により歪み硬化性パラメータ(λ)を得る。なお、粘度成長関数
については、以下の(B)式:
(ただしω=1/tとする。)で得られる。ここで、G’(ω)は角速度ωの関数としての貯蔵弾性率、G’(ω/2)はω/2の関数としての貯蔵弾性率、G”(ω)は各速度ωの関数としての損失弾性率、G”(ω/2)はω/2の関数としての損失弾性率、tは時間である。上記の歪み硬化性パラメータを得る方法は概要であり、当該歪み硬化性パラメータを得る方法の詳細については本願明細書の[実施例]の項目で記載する。
歪み硬化性パラメータが大きい場合、歪み硬化性が大きく、伸長変形に対する抵抗が大きい、すなわち分子鎖の絡まり合いの度合が大きいことを示す。歪み硬化性パラメータが小さい場合は歪み硬化性が小さく、分子鎖の絡まり合いの度合いが小さいことを示す。
歪み硬化現象は分岐をもつ高分子で観察され、分子収縮の阻害により、分子鎖、特に分岐点間の分子鎖セグメントの内部歪みが外部歪みに従って大きく増加するために生じる。また、主鎖セグメントの伸長に加え、分岐セグメントの圧縮によって生じる応力も歪み硬化に寄与する。
したがって、歪み硬化性パラメータは、高分子の分岐構造のみが異なる場合で、かつMolecular Stress Function(MSF)理論[W.H.Wagner、M.Yamaguchi、M.Takahashi、J.Rheol.,vol.47,p.779(2003)]に従うとすれば、分岐鎖の長さにより大きく変化し、分岐鎖が長いと大きくなる。
上記二軸延伸ポリプロピレンフィルムが、コンデンサ用として用いた場合に絶縁破壊の強さに優れるのは以下の理由による。但し、上記二軸延伸ポリプロピレンフィルムが上記効果に優れる理由について、仮に下記の理由とは異なっていたとしても、本発明の範囲内であることをここで明記する。
歪み硬化性パラメータ(非線形性パラメータ)が3未満のポリプロピレンは伸長粘度の歪み硬化性がほとんどないことを意味し、シートの薄肉部といった力学的に弱い部分が局所的に変形しやすい。したがって、このような延伸フィルムは厚み均一性が低いため、フィルムに存在する薄肉部において絶縁破壊が起こりやすく、絶縁破壊の強さの低下を招きやすい。逆に、歪み硬化性パラメータが20を超えるポリプロピレンでは、隣接高分子鎖によって、分岐鎖間の分子鎖収縮運動の阻害が顕著に現われることで、(a)自由体積の増加、(b)結晶欠陥やミクロボイドの発生、を招いてしまい、絶縁破壊の強さが上がりにくくなる。また、ゲルのような高度に分岐の発達した成分は歪み硬化性パラメータ3未満のポリプロピレンとの相溶性が低く、延伸操作によりゲル周囲にボイドによる絶縁欠陥が発生しやすくなる。そこで、歪み硬化性パラメータが3未満のポリプロピレンAと歪み硬化性パラメータ3以上20以下のポリプロピレンBとを組み合わせて樹脂成分とすることにより、上記ポリプロピレンAに起因する薄肉部の発生を抑えつつ、分岐鎖間の分子鎖収縮運動が阻害されない。その結果、当該フィルムをコンデンサ用として用いた場合に、絶縁破壊の強さを向上させることができる。
ポリプロピレンAの歪み硬化性パラメータは3未満である。
また、歪み硬化性パラメータが3以上の樹脂のみでフィルム成形を行うと、高引取り速度において分子鎖間の絡まり合いが顕著に現われ、成形中の熔融破断が発生しやすくなる。
(1)200mLのキシレンへ約1gの秤量された試料を投入し、120±5℃にて12時間加熱した。
(2)得られた液体を秤量された200メッシュ金網にて濾過した。
(3)濾過したメッシュを室温にて8時間、80℃にて3時間乾燥した。
(4)濾過したメッシュを秤量し、残渣の割合をゲル分率とした。
また、ポリプロピレンAの分子量分布(Z平均分子量/数平均分子量(Mz/Mn))は、より好ましくは25.0以上60.0以下、さらに好ましくは25.0以上50.0以下であり、特に好ましくは40.0以上50.0以下である。
キャピラリー:直径2.0mm、長さ40mm
シリンダー径:9.55mm
シリンダー押出速度:20mm/分
巻き取り速度:4.0m/分
温度:230℃
熔融張力が極めて高い場合には、引き取り速度4.0m/分では、樹脂が破断してしまう場合があり、このような場合には、引取り速度を下げ、引き取りのできる最高の速度における張力を熔融張力とした。
ポリプロピレンのような崩壊型ポリマーに過酸化物を添加すると、ポリマーからの水素引抜き反応が起こり、生じたポリマーラジカルは一部再結合し架橋反応も起こすが、殆どのラジカルは二次分解(β開裂)を起こし、より分子量の小さな二つのポリマーに分かれることが知られている。したがって、高分子量成分から高い確率で分解が進行し、よって、低分子量成分が増大し、分子量分布の構成を調整することができる。
ポリプロピレンBの歪み硬化性パラメータは3以上20以下である。歪み硬化性パラメータが20を超えるとフィルムに過剰な残留応力や異方性が生じ、耐衝撃性能や耐ストレスクラック性等の問題が生ずる。
また、ポリプロピレンBの歪み硬化性パラメータは、好ましくは18以下、より好ましくは16以下、さらに好ましくは14以下、特に好ましくは12以下である。ポリプロピレンBの歪み硬化性パラメータが20以下であれば、繰り返し混練による溶融張力の低下が起こりにくく、かつ伸長変形時の樹脂の歪み硬化性が維持されるため好ましい。
また、ポリプロピレンBの分子量分布(Z平均分子量/数平均分子量(Mz/Mn))は、好ましくは4.0以上9.0以下、より好ましくは4.2以上8.8以下、さらに好ましくは4.5以上8.5以下、特に好ましくは5.0以上8.2以下である。
カラムとして、いずれも東ソー株式会社製の、TSKgel guardcolumnHHR(30)(7.8mmID×7.5cm)と3本のTSKgel GMH-HR-H(20)HT(7.8mmID×30cm)とを連結して使用した。カラム温度を140℃に設定し、溶離液としてトリクロロベンゼンを1.0ml/分の流速で流して、MwとMnの測定値を得た。
本実施形態のフィルムに含まれるポリプロピレンAとポリプロピレンBの質量比率は、好ましくはポリプロピレンA:ポリプロピレンB=50:50~99.9:0.1、より好ましくは60:40~99:1、さらに好ましくは70:40~90:10、特に好ましくは75:25~85:15である。
本実施形態のフィルムを構成する樹脂成分全体に対するポリプロピレンA及びポリプロピレンBの合計質量%は、好ましくは90質量%以上、より好ましくは95質量%以上、さらに好ましくは99質量%以上、特に好ましくは100質量%(即ち、本実施形態のフィルムを構成する樹脂成分がポリプロピレンA及びポリプロピレンBの二種類であること)である。ポリプロピレンA及びポリプロピレンB以外の樹脂成分(他の樹脂成分)としては、ポリプロピレンA及びポリプロピレンBのいずれにも該当しないオレフィン系樹脂等が挙げられる。
本実施形態のフィルムは、樹脂成分に加えて、更に、添加剤を少なくとも1種含有してもよい。「添加剤」とは、一般的に、ポリプロピレンに使用される添加剤であって、本発明が目的とする二軸延伸ポリプロピレンフィルムを得ることができる限り特に制限されることはない。添加剤には、例えば、β晶造核剤、酸化防止剤、塩素吸収剤や紫外線吸収剤等の必要な安定剤、滑剤、可塑剤、難燃化剤、帯電防止剤等が含まれる。そのような添加剤を用いる場合、本実施形態のフィルムは、本発明が目的とする二軸延伸ポリプロピレンフィルムに悪影響を与えない量で添加剤を含むことができる。
本実施形態のフィルムの厚みは、好ましくは0.8μm以上50μm以下であり、より好ましくは1.0μm以上30μm以下であり、さらに好ましくは1.5μm以上20μm以下であり、特に好ましくは、1.7μm以上10μm以下であり、より特に好ましくは1.8μm以上7μm以下である。
また、本実施形態のフィルムの厚みは、15μmより大きく50μm未満であることも好ましい。本実施形態のフィルムの厚みは、より好ましくは16μmより大きく30μm未満であり、さらに好ましくは17μmより大きく20μm未満である。本実施形態のフィルムは、厚みが極めて薄いフィルムであることが好ましい。
本実施形態のフィルムの交流絶縁破壊の強さ(ES)は、好ましくは240[VAC/μm]以上、より好ましくは243[VAC/μm]以上、さらに好ましくは245[VAC/μm]以上である。
また、本実施形態のフィルムの直流絶縁破壊の強さ(ES)は、好ましくは465[VDC/μm]以上、より好ましくは470[VDC/μm]以上、さらに好ましくは480[VDC/μm]以上である。
本実施形態のフィルムのファーストランでの融点は、好ましくは166℃以上、より好ましくは168℃以上、さらに好ましくは169℃以上である。前記ファーストランでの融点が166℃以上であると、絶縁破壊の強さを保つために必要なラメラの厚みとなる。また、前記ファーストランでの融点は、好ましくは188℃以下、より好ましくは187℃以下、さらに好ましくは185℃以下である。前記ファーストランでの融点の上限は、ポリプロピレンの平衡融点(ラメラの厚みが無限大のときの融点)以下であり、成形加工性の観点から187℃以下が好ましい。前記ファーストランでの融点は、示差走査熱量測定のファーストランで求めた値であり、具体的には、実施例に記載の方法で測定される値である。
本実施形態のフィルムのファーストランでの融解エンタルピーは、好ましくは105J/g以上、より好ましくは106J/g以上、さらに好ましくは107J/g以上である。前記ファーストランでの融解エンタルピーが105J/g以上であると、絶縁破壊の強さを保つために必要な結晶化度となる。また、前記ファーストランでの融解エンタルピーは、好ましくは150J/g以下、より好ましくは130J/g以下、さらに好ましくは120J/g以下である。前記ファーストランでの融解エンタルピーが150J/g以下であると、適切な薄膜延伸性を有する。前記ファーストランでの融解エンタルピーは、示差走査熱量測定のファーストランで求めた値であり、具体的には、実施例に記載の方法で測定される値である。
本実施形態のフィルムのファーストランでの結晶化温度は、好ましくは112.8℃以上、より好ましくは112.9℃以上、さらに好ましくは113℃以上である。前記ファーストランでの結晶化温度が112.8℃以上であると、溶融押出した樹脂シートの冷却工程で生成する球晶サイズを小さく制御でき、延伸工程で生成する絶縁欠陥の生成を低く抑えることができる。また、前記ファーストランでの結晶化温度は、好ましくは125℃以下、より好ましくは123℃以下、さらに好ましくは122℃以下である。前記ファーストランでの結晶化温度が125℃以下であると、結晶変態による粗面形成が可能になる。前記ファーストランでの結晶化温度は、示差走査熱量測定のファーストランで求めた値であり、具体的には、実施例に記載の方法で測定される値である。
本実施形態のフィルムのファーストランでの結晶化エンタルピーは、好ましくは-150J/g以上、より好ましくは-130J/g以上、さらに好ましくは-120J/g以上、特に好ましくは-110J/g以上である。前記ファーストランでの結晶化エンタルピーが-150J/g以上であると、適切な薄膜延伸性を有する。また、前記ファーストランでの結晶化エンタルピーは、好ましくは-98J/g以下、より好ましくは-100J/g以下、さらに好ましくは-102J/g以下である。前記ファーストランでの結晶化エンタルピーが-98J/g以下であると、絶縁破壊の強さを保つために必要な結晶化度となる。前記ファーストランでの結晶化エンタルピーは、示差走査熱量測定のファーストランで求めた値であり、具体的には、実施例に記載の方法で測定される値である。
本実施形態のフィルムのセカンドランでの融点は、好ましくは160℃以上、より好ましくは161℃以上、さらに好ましくは162℃以上である。前記セカンドランでの融点が160℃以上であると、絶縁破壊の強さを保つために必要なラメラの厚みを有するフィルムを得やすい。また、前記セカンドランでの融点は、好ましくは188℃以下、より好ましくは170℃以下、さらに好ましくは165℃以下である。前記セカンドランでの融点が188℃以下であると、成形加工性の観点から好ましい。前記セカンドランでの融点は、示差走査熱量測定のセカンドランで求めた値であり、具体的には、実施例に記載の方法で測定される値である。
本実施形態のフィルムのセカンドランでの融解エンタルピーは、好ましくは95J/g以上、より好ましくは97J/g以上、さらに好ましくは98J/g以上である。前記セカンドランでの融解エンタルピーが95J/g以上であると、絶縁破壊の強さを保つために必要な結晶化度を得やすい。また、前記セカンドランでの融解エンタルピーは、好ましくは110J/g以下、より好ましくは105J/g以下、さらに好ましくは103J/g以下である。前記セカンドランでの融解エンタルピーが110J/g以下であると、適切な薄膜延伸性を有する。前記セカンドランでの融解エンタルピーは、示差走査熱量測定のセカンドランで求めた値であり、具体的には、実施例に記載の方法で測定される値である。
本実施形態の二軸延伸ポリプロピレンフィルムは、一般的に知られている二軸延伸ポリプロピレンフィルムの製造方法、例えばポリプロピレンAおよびポリプロピレンBを、必要に応じて他の樹脂および/または添加剤等と共に混合することにより得られたポリプロピレン樹脂組成物からキャスト原反シートを作製し、次いでキャスト原反シートを二軸延伸することにより製造することができる。
ポリプロピレン樹脂組成物を調製する方法としては、特に制限はないが、ポリプロピレンAおよびポリプロピレンBの重合粉あるいはペレットを、必要に応じて他の樹脂および/または添加剤等と共に、ミキサー等を用いてドライブレンドする方法や、ポリプロピレンAおよびポリプロピレンBの重合粉あるいはペレットを、必要に応じて他の樹脂および/または添加剤等と共に、混練機に供給し、溶融混練してメルトブレンド樹脂組成物を得る方法などがあるが、いずれでも構わない。
ポリプロピレン樹脂組成物が1次剤を含む場合、その含有量は、好ましくは樹脂成分の質量に対して(樹脂成分を全体としたときに質量で)1000質量ppm~5000質量ppmである。この目的の酸化防止剤は、押出機内での成形工程にてほとんどが消費され、製膜成形後のフィルム中には、ほとんど残存しない。
ポリプロピレン樹脂組成物がカルボニル基を有するヒンダードフェノール系酸化防止剤を含む場合、その含有量は、樹脂成分の質量に対して(樹脂成分を全体としたときに質量で)好ましくは100質量ppm~10000質量ppm、より好ましくは5500質量ppm~7000質量ppmである。押出機内では少なからず、カルボニル基を有するヒンダードフェノール系酸化防止剤も消費される。
ポリプロピレン樹脂組成物が1次剤を含まない場合、カルボニル基を有するヒンダードフェノール系酸化防止剤をより多く使用することができる。これは、押出機内で、カルボニル基を有するヒンダードフェノール系酸化防止剤の消費量が増えるためである。ポリプロピレン樹脂組成物が1次剤を含まず、カルボニル基を有するヒンダードフェノール系酸化防止剤を含む場合、その含有量は、樹脂成分の質量に対して(樹脂成分を全体としたときに質量で)6000質量ppm~8000質量ppm以下である。
キャスト原反シートは、予め作製したドライブレンド樹脂組成物および/またはメルトブレンド樹脂組成物のペレット類を押出機に供給して、加熱溶融し、ろ過フィルターを通した後、好ましくは170℃~320℃、より好ましくは200℃~300℃に加熱溶融してTダイから溶融押し出し、好ましくは40℃~140℃、より好ましくは80℃~140℃、さらに好ましくは90~140℃、特に好ましくは90~120℃、より特に好ましくは90~105℃の温度(キャスト温度)に保持された少なくとも1個以上の金属ドラムで、冷却、固化させることにより得ることができる。
本実施形態のフィルムは、上記キャスト原反シートに延伸処理を施すことによって製造することができる。延伸方法としては逐次二軸延伸方法が好ましい。逐次二軸延伸方法としては、まずキャスト原反シートを好ましくは100~180℃、より好ましくは140~160℃の温度に保ち、速度差を設けたロール間に通して流れ方向に3~7倍に延伸し、直ちに室温に冷却する。この縦延伸工程の温度を適切に調整することにより、β晶は融解しα晶に転移し、凹凸が顕在化する。引き続き、当該延伸フィルムをテンターに導いて好ましくは160℃以上、より好ましくは160~180℃の温度で幅方向に3~11倍に横延伸した後、緩和、熱固定を施して、巻き取る。
本実施形態は、別の態様では、ポリプロピレンフィルムの少なくとも片面に金属膜を有する金属化フィルムである。
実施例及び比較例のポリプロピレンフィルムを製造するために使用したポリプロピレン樹脂を以下の表1に示す。また、特に断らない限り、「部」及び「%」という記載は、それぞれ「質量部」及び「質量%」を示す。
ポリプロピレン樹脂Bとして、以下の表1に示す数平均分子量(Mn)、重量平均分子量(Mw)、z平均分子量(Mz)、分子量分布(Mw/Mn)、分子量分布(Mz/Mn)を有する下記の各ポリプロピレンを使用した。具体的には、
ポリプロピレンB1(日本ポリプロ株式会社製WAYMAX MFX6、メタロセン触媒を用いてプロピレンを重合することにより得られた長鎖分岐ポリプロピレン;以下、樹脂B1という)、
ポリプロピレンB2(日本ポリプロ株式会社製WAYMAX MFX8、メタロセン触媒を用いてプロピレンを重合することにより得られた長鎖分岐ポリプロピレン;以下、樹脂B2という)、
ポリプロピレンB3(日本ポリプロ株式会社製WAYMAX MFX3、メタロセン触媒を用いてプロピレンを重合することにより得られた長鎖分岐ポリプロピレン;以下、樹脂B3という)
を用いた。
ポリプロピレン樹脂B’として、
B’4(ボレアリスAG製Daploy WB135HMS、過酸化物による架橋変性により得られた長鎖分岐ポリプロピレン;以下、樹脂B’4という)、
を用いた。
表1に、ポリプロピレン樹脂A1及びB1~B’4の歪み硬化性パラメータ、重量平均分子量(Mw)、分子量分布(Mw/Mn)、分子量分布(Mz/Mn)を示した。
a)動的粘弾性測定
装置 :ARES-G2(ティー・エイ・インスツルメント社製)
治具 :コーンプレート(25mmφ、0.1rad.)
温度 :230℃
周波数 :100~0.01rad./sec.
b)伸長粘度測定
装置 :ARES-G2(ティー・エイ・インスツルメント社製)
治具 :伸長粘度フィクスチャー
温度 :230℃
歪み速度 :0.1/s。ただし、この条件でトルクが低く、伸長粘度が測定できない場合は、歪み速度を1.0/sとした。
予備歪み :0.2mm
測定手順:
(1)樹脂ペレットを230℃で5分間、熱プレス機を用いて加熱圧縮し、約0.6mmのプレスシートを作製した。得られたプレスシートをティー・エイ・インスツルメント社製のレオメータARES-G2を用いて剪断粘弾性測定(周波数分散)および伸長粘度測定を行った。
(2)剪断粘弾性測定(周波数分散)は、コーンプレート治具(25mmφ、0.1rad)へプレスシートを挟み、230℃で周波数100~0.01rad/secで測定した。
(3)伸長粘度測定は、伸長粘度測定治具を用いて230℃で、予備歪み0.2mmを与えた後に歪み速度0.1/sで測定した。なお、この条件でトルクが低く、伸長粘度が測定できない場合は、歪み速度を1.0/sとした。上記伸長粘度測定治具は、熔融ポリマー等の高粘性物質の伸長粘度を測定するための治具であり、一定のHenky歪み速度で引っ張ることができるように、固定部と回転ドラムから構成されている。
(4)剪断粘弾性測定(周波数分散)により得られたデータを、「尾崎邦宏 村井朝 別所信夫 金鳳植 日本レオロジー学会誌 4巻 166(1976)」の記載の方法に基づき、次式(B)に示される粘度成長関数
を求めた。
ただしω=1/tとする。
ここで、G’(ω)は角速度ω の関数としての貯蔵弾性率、G’(ω/2)はω/2の関数としての貯蔵弾性率、G”(ω)は角速度ω の関数としての損失弾性率、tは時間である。
(5)一方、伸長粘度測定により得られた非定常一軸伸長粘度曲線ηE(t)において、歪の大きさが2以上で伸長粘度が最大となる点における時間をtmaxとし、下記式(A)により伸長粘度の非線形性パラメータ、すなわち歪み硬化性パラメータ(λ)を求めた。なお、λについての概念図を図1に示した。
(6)なお、式(B)により得られる粘度成長関数と、非定常一軸伸長粘度曲線との間で、短時間側の線形領域の重なりが悪い場合には、非定常一軸伸長粘度曲線における線形部分の中点付近が重なるようにシフトさせてから歪み硬化性パラメータλを求めた。これは、伸長粘度測定において、歪の開放等で想定値よりも断面積が増加する場合、粘度が小さいために試料が垂れ下がり断面積が低下する場合があるため、その誤差を軽減するための措置である。
各樹脂のゲル分率の測定条件は、以下の通りとした。
試料量 :約1g
溶媒 :キシレン(200mL)
加熱温度 :120℃
加熱時間 :12時間
ろ過メッシュ :200メッシュ金網
乾燥 :室温×8時間+80℃×3hr
200mLのキシレンへ約1gの秤量された試料を投入し、120℃にて12時間加熱した。得られた液体を秤量された200メッシュ金網にて濾過した。濾過したメッシュを室温にて8時間、80℃にて3時間乾燥した。濾過したメッシュを秤量し、残渣の割合をゲル分率とした。
GPC(ゲルパーミエーションクロマトグラフィー)を用い、以下の条件で、ポリプロピレンの数平均分子量(Mn)、重量平均分子量(Mw)、z平均分子量(Mz)、分子量分布(Mw/Mn)、分子量分布(Mz/Mn)、分布曲線の微分分布値を測定した。
東ソー株式会社製、示差屈折計(RI)内蔵型高温GPC装置であるHLC-8121GPC-HT型を使用した。カラムとして、東ソー株式会社製のTSKgelGMHHR-H(20)HTを3本連結し、さらに、TSKgel guardcolumnHHR(30)1本使用した。140℃のカラム温度で、溶離液として、1,2,4-トリクロロベンゼンに0.05wt%の2,6-ジ-ターシャリー-ブチル-パラ-クレゾール(一般名称:BHT)を、1.0ml/minの流速で流して測定し、数平均分子量(Mn)、重量平均分子量(Mw)及びz平均分子量(Mz)を得た。このMzとMnの値を用いて分子量分布(Mz/Mn)を、また、MwとMnの値を用いて分子量分布(Mw/Mn)を得た。測定条件は、以下の通りである。
GPC装置 :HLC-8121GPC/HT(東ソー製)
光散乱検出器:DAWN EOS(Wyatt Technology社)、
カラム :TSKgel guardcolumnHHR(30)(7.8mmID×7.5cm)×1本+TSKgel GMHHR-H(20)HT(7.8mmID×30cm)×3本(東ソー製)
溶離液 :1,2,4-トリクロロベンゼンに0.05wt%のBHT
流速 :1.0mL/min
試料濃度 :2mg/mL
注入量 :300μL
カラム温度 :140℃
システム温度:40℃
前処理 :試料を精秤し、溶離液を加えて140℃で1時間振とう溶解させ、0.5μmの焼結金属フィルターで熱ろ過を行った。
微分分布値の差は、次のような方法で得た。まず、RI検出計を用いて検出される強度分布の時間曲線(溶出曲線)を、上記標準ポリスチレンを用いて作製した検量線を用いて標準ポリスチレンの分子量M(Log(M))に対する分布曲線に変換した。次に、分布曲線の全面積を100%とした場合のLog(M)に対する積分分布曲線を得た後、この積分分布曲線をLog(M)で、微分することによってLog(M)に対する微分分布曲線を得ることが出来た。この微分分布曲線から、Log(M)=4.5およびLog(M)=6.0のときの微分分布値を読んだ。なお、微分分布曲線を得るまでの一連の操作は、使用したGPC測定装置に内蔵されている解析ソフトウェアを用いて行った。また、微分分布値の測定及び微分分布値の差の算出は、上記樹脂A1に対してのみ行った。
測定及び算出の結果、樹脂A1の上記微分分布値の差(Log(M)=4.5のときの微分分布値に対してLog(M)=6.0のときの微分分布値を引いた、差)は、11.7であった。
ポリプロピレンを溶媒に溶解し、高温型フーリエ変換核磁気共鳴装置(高温FT-NMR)を用いて、以下の条件で、メソペンタッド分率([mmmm])を求めた。
測定機:日本電子株式会社製、高温FT-NMR JNM-ECP500
観測核:13C(125MHz)
測定温度:135℃
溶媒:オルト-ジクロロベンゼン〔ODCB:ODCBと重水素化ODCBの混合溶媒(4/1)〕
測定モード:シングルパルスプロトンブロードバンドデカップリング
パルス幅:9.1μsec(45°パルス)
パルス間隔:5.5sec
積算回数:4500回
シフト基準:CH3(mmmm)=21.7ppm
5連子(ペンタッド)の組み合わせ(mmmmやmrrmなど)に由来する各シグナルの強度積分値より、百分率(%)で算出した。mmmmやmrrmなどに由来する各シグナルの帰属に関し、例えば、「T.Hayashiet al.,Polymer,29巻,138頁(1988)」などのスペクトルの記載を参考とした。なお、メソペンタッド分率の測定は、上記樹脂A1に対してのみ行った。樹脂A1のメソペンタッド分率は、97.8%であった。
JIS K 7210:1999に準じて、測定温度230℃にて、株式会社東洋精機製作所製メルトインデクサーを用いて測定した。
東洋精機社製キャピログラフ1Bを用い、下記の条件で樹脂を紐状に押し出して、ローラーに巻き取っていった時にプーリーに検出される張力を、溶融張力とした。
キャピラリー:直径2.0mm、長さ40mm
シリンダー径:9.55mm
シリンダー押出速度:20mm/分
巻き取り速度:4.0m/分
温度:230℃
熔融張力が極めて高い場合には、引き取り速度4.0m/分では、樹脂が破断してしまう場合があり、このような場合には、引取り速度を下げ、引き取りのできる最高の速度における張力を熔融張力とする。
樹脂A1と樹脂B1をA1/B1=80/20(質量比)で、連続的に計量し混合したドライブレンド樹脂組成物を、押出機に供給した。ドライブレンド樹脂組成物を230℃の温度で溶融した後、Tダイを用いて押出し、表面温度(キャスト温度)を45℃に保持した金属ドラムに巻きつけて固化させて、厚さ900μmのキャスト原反シートを製造した。このキャスト原反シートをBrueckner社製バッチ式二軸延伸機KARO IVを用いて165℃で、流れ方向に5倍、次いで横方向に10倍に延伸して、厚さ18μmの二軸延伸PPフィルムを得た。樹脂の配合比と得られたフィルムの物性値を表2にまとめた。
樹脂B1に代えて樹脂B2を用いたこと以外は、実施例1と同様にして二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの厚さは18μmであった。樹脂の配合比と得られたフィルムの物性値を表2にまとめる。
樹脂A1と樹脂B1を表1に記載の質量比で用いたこと以外は、実施例1と同様にして二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの厚さは18μmであった。樹脂の配合比と得られたフィルムの物性値を表2にまとめる。
樹脂B1に代えて樹脂B2を用いたこと以外は、実施例3と同様にして二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの厚さは18μmであった。樹脂の配合比と得られたフィルムの物性値を表2にまとめる。
樹脂B1に代えて樹脂B3を用いたこと以外は、実施例1と同様にして二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの厚さは18μmであった。樹脂の配合比と得られたフィルムの物性値を表2にまとめる。
樹脂A1と樹脂B1をA1/B1=98/2(質量比)で、連続的に計量し混合したドライブレンド樹脂組成物を、押出機に供給した。ドライブレンド樹脂組成物を250℃の温度で溶融した後、Tダイを用いて押出し、表面温度(キャスト温度)を95℃に保持した金属ドラムに巻きつけて固化させて厚さ100μmのキャスト原反シートを製造した。この未延伸のキャスト原反シートを140℃の温度に保ち、速度差を設けたロール間に通して流れ方向に4.5倍に延伸し、直ちに室温に冷却した。引き続き、当該延伸フィルムをテンターに導いて、横延伸温度158℃で幅方向に10倍に延伸した後、緩和、熱固定を施して、厚み2.5μmの二軸延伸ポリプロピレンフィルムを巻き取った。
樹脂成分として樹脂A1のみを単独で用いたこと以外は、実施例1と同様にして二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの厚さは18μmであった。樹脂の配合比と得られたフィルムの物性値を表2にまとめる。
樹脂B1に代えて樹脂B’4を用いたこと以外は、実施例1と同様にして二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの厚さは18μmであった。樹脂の配合比と得られたフィルムの物性値を表2にまとめる。
樹脂成分として樹脂B1のみを単独で用いたこと以外は、実施例1と同様にして二軸延伸ポリプロピレンフィルムを得ようとしたところ、押出成形時のメルトフラクチャーにより平滑なキャストシートが作製できなかった。そのため、得られたキャストシートを延伸した時に破断が起こり、延伸フィルムを得られなかった。
樹脂成分として樹脂B2のみを単独で用いたこと以外は、実施例1と同様にして二軸延伸ポリプロピレンフィルムを得ようとしたところ、押出成形時のメルトフラクチャーにより平滑なキャストシートが作製できなかった。そのため、得られたキャストシートを延伸した時に破断が起こり、延伸フィルムを得られなかった。
樹脂A1と樹脂B1のドライブレンド体に代えて樹脂A1のみを使用したとした以外は、実施例6と同様にして、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの厚さは2.5μmであった。樹脂の配合比と得られたフィルムの物性値を表2にまとめる。
樹脂A1と樹脂B1のドライブレンド体に代えて樹脂A1と樹脂B’4のドライブレンド体(A1/B’4=98/2(質量比))を使用したとした以外は、実施例6と同様にして、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの厚さは2.5μmであった。樹脂の配合比と得られたフィルムの物性値を表2にまとめる。
実施例及び比較例における特性値の測定方法等は以下の通りである。
マイクロメーター(JIS-B7502)を用いて、JIS-C2330に準拠して測定した。
二軸延伸フィルムの耐電圧性は、JIS C 2330:2010及びJIS C 2151:2006 17.2.2(絶縁破壊電圧・平板電極法)に準じて絶縁破壊の強さ(ES)を測定した。雰囲気温度100℃にて測定を行った。昇圧速度は100Vac/sec、破壊の際の遮断電流は10mAとし、測定回数は18回とした。ここでは、測定された平均電圧値を、フィルムの厚みで割ったものを、絶縁破壊強度として評価に用いた。送風循環式高温槽内にフィルム及び電極冶具をセットして、評価温度100℃にて、測定を行った。
なお、実施例1~5、及び、比較例1~2については、交流絶縁破壊の強さ(ES)を測定し、実施例6、比較例5、及び、比較例6については、直流絶縁破壊の強さ(ES)を測定した。一般的に、交流で電圧をかける方が直流で電圧をかけるよりも負荷は高い。そこで、厚さ18μmの実施例1~5、及び、比較例1~2については、直流で測定すると負荷が充分とならず、適切な評価ができないため、交流で測定した。一方、厚さ2.5μmの実施例6、比較例5、及び、比較例6は、直流にて充分な負荷を与えることができるため、直流で測定した。
実施例、比較例の二軸延伸ポリプロピレンフィルムから5mgの試料を切り出し、アルミニウム製パンに封入し、示差走査熱量計(パーキン・エルマー社製のDiamondDSC)で入力補償示差走査熱量測定をおこなった。測定では、窒素雰囲気下で30℃から280℃まで20℃/分で昇温(ファーストラン)した。ファーストランの結果から、融点、融解エンタルピー、結晶化温度、及び、結晶化エンタルピーを求めた。
ファーストランの後、280℃で5分間保持した後、降温速度20℃/分の条件で30℃まで冷却し、30℃で5分間保持した。その後、窒素雰囲気下で30℃から280℃まで20℃/分で昇温(セカンドラン)した。セカンドランの結果から、融点、及び、融解エンタルピーを求めた。
各実施例の二軸延伸ポリプロピレンフィルムの表面に、Tマージン蒸着パターンを蒸着抵抗12Ω/□にてアルミニウム蒸着により施して金属膜を形成し、金属化フィルムを得た。小幅にスリットした後に、2枚の金属化フィルムを相合わせて、株式会社皆藤製作所製、自動巻取機3KAW-N2型を用い、巻き取り張力200gにて、1360ターン巻回を行った。
素子巻きした素子は、プレスしながら120℃にて4時間熱処理を施した後、素子端面に亜鉛金属を溶射し、扁平型コンデンサを得た。出来上がったコンデンサの静電容量は、100μF(±5μF)であった。
Claims (10)
- 歪み硬化性パラメータが3未満であるポリプロピレンAと、
歪み硬化性パラメータが3以上20以下であるポリプロピレンBと
を樹脂成分として含有することを特徴とする、二軸延伸ポリプロピレンフィルム。 - 前記ポリプロピレンBは長鎖分岐ポリプロピレンである、請求項1に記載の二軸延伸ポリプロピレンフィルム。
- 前記ポリプロピレンBのゲル分率は、前記ポリプロピレンBの質量を基準に1000質量ppm以下である、請求項1または2に記載の二軸延伸ポリプロピレンフィルム。
- 前記ポリプロピレンBは、メタロセン触媒を用いてプロピレンを重合することにより得られたものである、請求項1~3のいずれか1に記載の二軸延伸ポリプロピレンフィルム。
- 前記ポリプロピレンBの分子量分布(Mw/Mn)は1.5以上4.5以下である、請求項1~4のいずれか1に記載の二軸延伸ポリプロピレンフィルム。
- 前記ポリプロピレンAとポリプロピレンBの質量比率は、ポリプロピレンA:ポリプロピレンB=50:50~99.9:0.1である、請求項1~5のいずれか1に記載の二軸延伸ポリプロピレンフィルム。
- 前記ポリプロピレンAの分子量分布(Mw/Mn)は7.0以上12.0以下である、請求項1~6のいずれか1に記載の二軸延伸ポリプロピレンフィルム。
- コンデンサ用である、請求項1~7のいずれか1に記載の二軸延伸ポリプロピレンフィルム。
- 請求項1~8のいずれか1に記載のポリプロピレンフィルムの少なくとも片面に金属膜を有する金属化フィルム。
- 請求項9に記載の金属化フィルムを含むコンデンサ。
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