CN106459448A - Stretched film - Google Patents

Abstract

Provided is a syndiotactic polystyrene-based resin alignment film having excellent windability and shaving resistance or a stretched film that is suitable for use in particular as a film capacitor and has excellent particle dispersibility, dielectric breakdown characteristics, shaving resistance, and handling properties including windability. Specifically, the stretched film comprises a resin composition that contains a syndiotactic styrene-based polymer and also contains porous particles having an average particle diameter of 0.5-5.0 [mu]m, and the content of the porous particles being 0.01-3 mass% relative to the mass of the resin composition. The stretched film satisfies either of the following conditions: (1) the resin composition contains a silicone oil, with the content of the silicone oil being 0.1-3 mass% relative to the mass of the porous particles; or (2) the porous particles are porous silica particles having an average particle diameter A of 0.5-5 [mu]m and a di-n-butylamine adsorption (DBA) value of 200 millimoles/kg or less.

Description

Stretched film

Technical field

First, the present invention relates to advising the alignment films of the styrenic of (syndiotactic) structure between comprising, enters one Step specifically, is related to windability and the improved styrenic comprising syndiotactic structure of scratch stretched film.

Second the present invention relates to the stretching of the improved resin combination of dispersibility comprising porous silica silicon grain Film.Further specifically, it is related to comprise the operability such as windability of resin combination, resistance to scraping (resistance to cut れ), medium hit Wear the stretched film that characteristic is improved, be particularly suitable for thin film capacitor, in this resin combination, porous silica Dispersibility in the polystyrene resin of syndiotactic structure for the grain is improved.

Background technology

In the past, thin film capacitor manufactured by the following method：By biaxial orientation polyethylene glycol terephthalate's thin film, double The thin film such as axle oriented polypropylene films are overlapping with metallic films such as aluminium foils, and be wound or lamination method.In recent years, with Circuit or the requirement of electronic circuit miniaturization, the miniaturization of thin film capacitor, assemblingization also develop, except electrical characteristic with Require outward and then also thermostability.In addition, in mobile applications, not only driving indoor use, range is also extend to start Machine is indoor, in addition to electrical characteristic, also requires the thin film capacitor of the environment under suitable high humidity at higher temperature.

For above-mentioned requirements, Japanese Unexamined Patent Publication H02-143851 publication, Japanese Unexamined Patent Publication H03-124750 publication, Japan are special Open H05-200858 publication, propose using thermostability and electrical characteristic in No. 2008/156210 pamphlet of International Publication No. The method of excellent styrene-based thin film.But, masking is difficult compared with the conventional mylar using, and thin film Easy to crack, therefore also require improvement to manufacture treatability during capacitor.As the method for such improvement Film making properties, treatability, lead to Often in resin, coordinate powder stuffing, but conventionally used powder stuffing be when making thin film by styrene-based resin, It is difficult to take into account windability and resistance to scraping.

In addition, being directed to above-mentioned requirements, propose in Japanese Unexamined Patent Publication 2000-173855 publication using thermostability than poly- to benzene Naphthalate thin film or the more excellent polyethylene glycol 2，6-naphthalene dicarboxylate thin film of polypropylene film, control its crystalloid The method to improve electrical characteristic such as state, intrinsic viscosity.But, because polyethylene glycol 2，6-naphthalene dicarboxylate is polar polymeric The improvement of thing, therefore electrical characteristic is limited.

Prior art literature

Patent documentation

Patent documentation 1：Japanese Unexamined Patent Publication H02-143851 publication

Patent documentation 2：Japanese Unexamined Patent Publication H03-124750 publication

Patent documentation 3：Japanese Unexamined Patent Publication H05-200858 publication

Patent documentation 4：No. 2008/156210 pamphlet of International Publication No.

Patent documentation 5：Japanese Unexamined Patent Publication 2000-173855 publication.

Content of the invention

Problems to be solved by the invention

First present invention completes in view of the aforementioned technical background, between its object is to provide windability and resistance to scraping excellent The stretched film of stereospecific polymerized styrene system resin.

Second present invention completes in view of the aforementioned technical background, its object is to provide the polyphenyl second in syndiotactic structure The operability such as the particle dispersion in alkene system resin is excellent, windability, resistance to scraping, dielectric breakdown characteristic (dielectric breakdown voltage, its Deviation) stretched film excellent, that thin film capacitor can be particularly suitable for.

Should illustrate, the stretched film of the present invention is properly termed as making the alignment films of molecular chain orientation by stretching, exists below It is otherwise referred to as alignment films in first present invention.

For solution to problem

The present inventor has made intensive studies to various inert particles to achieve these goals.In research, to can press down The porous particle of the generation of the void such as polyester processed has been also carried out studying, but styrene-based resin cannot obtain and gather The same effect such as ester film.However, it is surprising that the inventors discovered that by porous particle and silicone oil and with after, can Solve the above problems, thus completing first present invention.

Thus, according to first present invention, provide a kind of stretched film (being referred to as alignment films below in first present invention), this draws Stretch film and comprise resin combination, this resin combination contains the styrenic of syndiotactic structure, mean diameter is 0.5 ~ 5.0 μm porous particle and silicone oil, wherein, on the basis of the quality of this resin combination, the content of porous particle is 0.01 matter Scope below amount more than % and 3 mass %, on the basis of the quality of this porous particle, the content of silicone oil is the model of 0.1 ~ 3 mass % Enclose.

In addition, the present inventor has made intensive studies to achieve these goals, it was found that it is special to have particular surface Property porous silica silicon grain resin combination in the polystyrene resin of syndiotactic structure for the cooperation can be easy Ground obtain this granule dispersibility excellent and also as needed with matrix resin dilute and form the space producing during stretched film Little, as also good stretched film such as thin film capacitor used time operability, dielectric breakdown characteristic, resistance to scrapings, thus completing Two present invention.

Thus, according to second present invention, provide a kind of stretched film, this stretched film comprises resin combination, this resin combination Polystyrene resin that thing contains syndiotactic structure and mean diameter A are 0.5 ~ 5 μm, DBA value is 200 mMs/below kg Porous silica silicon grain, wherein, on the basis of resin combination amount of substance, the content of this porous silica silicon grain is 0.01 More than quality % and below 3 mass %.

As described above, according to the present invention, providing above-mentioned first present invention and second present invention.Specifically, provide one kind It is characterised in that this stretched film comprises resin combination, the polystyrene that this resin combination contains syndiotactic structure gathers stretched film Compound and mean diameter are 0.5 ~ 5.0 μm of porous particle, on the basis of the quality of this resin combination, the content of porous particle For the scope more than 0.01 mass % and below 3 mass %, described stretched film meets any one of following (1), (2)：

(1) resin combination contains silicone oil, and on the basis of the quality of this porous particle, the content of silicone oil is the model of 0.1 ~ 3 mass % Enclose；Or

(2) porous particle be mean diameter A be 0.5 ~ 5 μm, the porous silica for 200 mMs/below kg for the DBA value Grain.

The effect of invention

The stretched film of first present invention is gathered in the polystyrene with syndiotactic structure using electrical characteristic and excellent heat resistance Additionally it is possible to make the alignment films of gained possess the windability of height and resistance to scraping while compound.

In addition, according to first present invention, dielectric breakdown voltage height can also be obtained and the little orientation of its standard deviation Film, also can be suitable as the basement membrane (base film) of the thin film capacitor of very thin and difficult operation.

The stretched film of second present invention, in the polystyrene resin of thermostability and the syndiotactic structure of excellent electrical characteristic The porous silica silicon grain with specified particle diameter and particular surface property containing specified quantitative, therefore the dispersibility pole of this granule Good, and the space producing because of this granule is little, and operability, dielectric breakdown characteristic, resistance to scraping are excellent, are particularly suitable as thin film Capacitor is used.

Specific embodiment

First, the alignment films of first present invention are illustrated.

The alignment films of the present invention comprise resin combination, and this resin combination contains the polystyrene polymerization of syndiotactic structure Thing, mean diameter are 0.5 ~ 5.0 μm of porous particle and silicone oil.

Polystyrene resin (hereinafter sometimes referred to " the syndiotactic polytyrene tree with syndiotactic structure in the present invention Fat " or " SPS ") it is the resin with following stereochemical structure：With respect to the main chain by carbon-carbon bond formation, as the benzene of side chain Base, substituted-phenyl are alternately located in rightabout.Generally steric regularity (tacticity) is common by using the nuclear-magnetism of isotope carbon Shake method (¹³C-NMR method) carry out quantitation.Specifically, can be represented with the presence ratio of continuously multiple construction units, for example Exist and represented with diad (diad) when 2, exist and represented with triad (triad) when 3, exist when 5 with five lists Tuple (pentad) represents.The polystyrene resin of the syndiotactic structure in the present invention refers to, have diad be 75% with Above, it is preferably more than 85%, or five unit groups are more than 30%, are preferably more than 50% polystyrene of degree of syndiotacticity, gather (ring-alkylated styrenes), poly- (halogenated styrenes), poly- (alkoxystyrene), poly- (vinyl benzoate) or their phenyl ring The polymer that is hydrogenated of a part or their mixture, also or the copolymer containing these construction units.Should say Bright, herein as poly- (ring-alkylated styrenes), including poly- (methyl styrene), poly- (ethyl styrene), poly- (propylstyrene), poly- (butylstyrene), poly- (styryl phenyl) etc., as poly- (halogenated styrenes), including poly- (chlorostyrene), poly- (bromobenzene second Alkene), poly- (fluorobenzene ethene) etc..In addition, as poly- (alkoxystyrene), including poly- (methoxy styrene), poly- (ethoxybenzene Ethylene) etc..

Wherein, as preferred polystyrene resin, can include polystyrene, poly- (p-methylstyrene), poly- ( Methyl styrene), poly- (p-tert-butylstyrene), poly- (to chlorostyrene), poly- (m-chlorostyrene), poly- (pfluorostyrene), And the copolymer of styrene and p-methylstyrene, wherein preferably polystyrene.

And then, in the case of using as copolymer containing copolymer composition in the polystyrene resin of the present invention, as Its comonomer, in addition to the monomer of polystyrene resin as above, can also using ethylene, propylene, butylene, oneself The olefinic monomers such as alkene, octene, the diene monomers such as butadiene, isoprene, cyclic diene monomer or methyl methacrylate, horse Come anhydride, acrylonitrile isopolarity vinyl monomer etc..

In addition, the weight average molecular weight of the polystyrene resin of this syndiotactic structure is preferably 1.0 × 10⁴~3.0×10⁶, enter One step is preferably 5.0 × 10⁴~1.5×10⁶, particularly preferably 1.1 × 10⁵~8.0×10⁵.By making weight average molecular weight be 1.0 ×10⁴Above, it is preferably 5.0 × 10⁴Above, particularly preferably 1.1 × 10⁵More than, strength elongation characteristic can be obtained excellent The formed products such as the thin film that different, thermostability improves further.In addition, if weight average molecular weight is 3.0 × 10⁶Below, it is preferably 1.5 ×10⁶Below, particularly preferably 8.0 × 10⁵Hereinafter, then make tensile stress in optimum range, be not susceptible to during masking etc. rupture Deng.

Contained porous particle in the alignment films of the present invention, needs its mean diameter to be 0.5 ~ 5 μm, be preferably 0.8 ~ 2.5 μ m.In the case that its mean diameter is less than 0.5 μm, the smoothness (sliding り) of thin film is not enough, and windability and operability is insufficient. On the other hand, in the case of more than 5 μm, the diameter in the space being formed around granule because of stretching etc. becomes big, and it is not preferable. In addition, on the basis of resin combination amount of substance, the content needing this granule is 0.01 ~ 3 mass %, is more preferably 0.02 ~ 1 The scope of quality %, particularly preferably 0.05 ~ 0.5 mass %.If its content deficiency lower limit, smoothness is not enough and windability shortage. On the other hand, in the case of exceeding the upper limit, in addition to resistance to scraping is insufficient, also impair dielectric breakdown characteristic, masking is drawn Stretching property.

From the above point of view, the mean diameter of porous particle used in the present invention be preferably 0.5 ~ 5 μm, excellent further Elect 0.8 ~ 2.5 μm as.And then, in the present invention, the compression ratio of porous particle used is (during 0.2gf load：Using Shimadzu Seisakusho Ltd. Slight compression processed is tested MCTM-200 and is measured) it is preferably 20 ~ 90%, particularly preferably 50 ~ 85% scope.This value not foot In the case of limit, such as when making stretched film, the raising of resistance to scraping is not sufficiently effective.On the other hand, in the case of exceeding the upper limit, example During as made stretched film, this granule is pulverized and is made to convex to form insufficient, windability raising effect and diminish.By making compression ratio In above-mentioned proper range, this granule due to be processed into stress during stretched film etc. and appropriateness deformation so that easily more highly Take into account windability and resistance to scraping.

As such porous particle, it is possible to use granule commonly known per se, particularly preferably include porous silica Granule.The manufacture method of porous silica silicon grain is not particularly limited, it is possible to use existing by sol-gal process, sedimentation method etc. There is the known granule that known method is made.Wherein, preferably pore volume is 0.4 ~ 2.5ml/g, is particularly preferably 1.2 ~ 1.8ml/g Scope granule, additionally, it is preferred that average pore size be 5 ~ 25nm scope granule.

As described above, the alignment films of the present invention also and use silicone oil.On the basis of the quality of this porous particle, the containing of this silicone oil The scope measure as 0.1 ~ 3 mass %, being preferably 0.2 ~ 2.0 mass %.In the case of the content deficiency lower limit of silicone oil, this porous particle Dispersibility be deteriorated and form thick agglutinating particle and make masking draftability bad, resistance to scraping is not sufficiently effective in addition.On the other hand, exist In the case of exceeding the upper limit, sometimes can ooze out silicone oil on the surface of thin film and pollute manufacturing procedure.

Silicone oil referred to herein refers to, the organo-silicon compound with dialkylsiloxane composition as predominant repeat unit, can arrange Enumerate the silicone oil of the linear chain structure that siloxanes key is less than 2000.For example can include：The side chain of polysiloxanes, end are first A part for the dimethyl polysiloxane of base and then polysiloxanes side chain is the methyl phenyl silicone of phenyl, polysiloxanes A part for side chain is the pure silicons such as the methylhydrogenpolysi,oxane of hydrogen oil (straight silicone oil, common silicone oil)；Other Introduce the modified silicon oil of organic group in side chain, end.As introduced organic group in modified silicon oil, can include： Monoamine base, two amidos, amino, epoxy radicals, aliphatic ring epoxide, sulfydryl, carboxyl, polyether-based, aralkyl, fluoroalkyl, long alkane Base, higher fatty acids ester group, higher fatty acid amides base, methylacryloyl, carboxyl, phenolic group, silanol group etc..Wherein, from From the aspect of excellent heat resistance, preferably dimethyl polysiloxane.

Silicone oil fitting method in the film is not particularly limited, from being easy to make silicone oil optionally be present in above-mentioned porous It is preferred that after direct Deca or coating, spraying spraying etc. in above-mentioned porous particle, putting from the viewpoint of particle surface The method entering stirring in mixer etc..

Porous particle after processing through silicone oil attachment can add in the polymerization stage of resin material, it would however also be possible to employ melting Compounding process is added in the resin material by polymerization gained, need not be particularly limited to.For example, it may be by this porous particle powder body The method supplying and carrying out melting mixing from the same supply mouth of melting mixing machine with resin material；Or first to band steam vent (vent) put into resin material in the melting mixing machine such as twin-screw mixer extruder, then this porous particle is added to powder body Position that this resin material has melted the method carrying out melting mixing.Wherein, this granule and the tree of silicone oil will be preferably attached with After fat granule material (resin pellet) or toner are pre-mixed, it is supplied in the twin-screw mixer extruder with steam vent Method.According to the method thus it is speculated that because this granule is attached to the surface of resin granular material or toner, therefore inside kneading machine When being pulverized, this granule is minimum with the contact interval of resin, so dispersibility improves further.

As the twin-screw mixer extruder with steam vent, preferably use following device：The interpolation mouth of granule is arranged on joins It is placed in full thread (full flight) portion of the screw rod within the twin-screw mixer extruder with steam vent, from above-mentioned interpolation It is provided with least the one of opening's edge screw rod axis direction downstream and have for making granule knead scattered feeding blade (sending the り wing) With the rotor segment (rotor segment) returning blade (the wing).Herein, gas exhaust piping (vent line) is used for removing By-product from resin.In addition, the twin-screw mixer extruder with steam vent preferably has rotor segment at 1 ~ 3.If irrotationality The mixing dispersion turning scraper plate then this granule reduces, if rotor segment more than 3 at; the propulsive force of resin reduce and easily occurs curved Folding (bent up).Additionally, it is preferred that having the scattered kneading disk of mixing for supplementing this porous particle.

For the alignment films of the present invention, in thin film greatest length be more than 25 μm of thick agglutinating particle quantity excellent Elect 10/m as²Hereinafter, more preferably 5/m²Hereinafter, particularly preferably 3/m²Below.The number of thick agglutinating particle If being more than the upper limit, film surface produces uneven projection, and winding skew when making stretch wrap film (returning Off ィ Le system) becomes Difference, processability reduce, therefore are not suitable for.In addition, becoming the starting point of fracture in masking stretching process, draftability is unstable, therefore not Preferably.

In the range of without prejudice to the object of the invention, the alignment films of the present invention are acceptable in addition to adding this porous particle Add the granule Bs different from this porous particle.Because above-mentioned porous particle can form larger projection, the therefore preferred present invention's Granule B plays and forms less raised role.From this viewpoint, the particle diameter of preferably granule B is less than above-mentioned porous particle, by In the little therefore preferably not agglutinophilic granule of particle diameter.Mean diameter A of granule B is preferably 0.01 μm less than 0.5 μm.Enter One step is preferably 0.1 μm less than 0.4 μm.If mean diameter A deficiency lower limit, sufficient smoothness cannot be obtained, It is not preferable.On the other hand, if mean diameter A exceedes the upper limit, resistance to scraping is deteriorated, and it is not preferable.

On the basis of the quality of alignment films, the content of the granule B of the present invention is preferably below 0.5 weight %.If content mistake Many, then the frequency in space produced by granule increases or dielectric breakdown voltage reduces sometimes.From this viewpoint, further It is preferably below 0.5 weight %, be particularly preferably below 0.2 weight %.

Species as granule B, it is possible to use the little spherical particle of various granules, preferably specific surface area.Should illustrate, The spherical of the present invention refers to, when carrying out image analysis to the shape of granule, maximum major diameter is 1.5 with the ratio of area diameter of equivalent circle Below, it is preferably less than 1.2 shape.As concrete granule, it is not particularly limited, can include (1) two known to itself Silicon oxide (includes hydrate, silica sand, quartz etc.)；(2) aluminium oxide of various crystal habits；(3) contain the above SiO of 30 weight %₂ Silicate (clay mineral of such as amorphous state or crystalline state, aluminosilicate (including calcined material, hydrate), chrysotile, the zirconium of composition Stone, flyash etc.)；(4) oxide of Mg, Zn, Zr and Ti；(5) sulfate of Ca and Ba；(6) phosphate of Li, Ba and Ca (including monohydric salt and dihydric salt)；(7) benzoate of Li, Na and K；(8) terephthalate of Ca, Ba, Zn and Mn；(9) The titanate of Mg, Ca, Ba, Zn, Cd, Pb, Sr, Mn, Fe, Co and Ni；(10) chromate of Ba and Pb；(11) carbon (such as charcoal Black, graphite etc.)；(12) glass (such as glass dust, bead etc.)；(13) carbonate of Ca and Mg；(14) fluorite；(15) point is brilliant Stone-type oxide；(16) crosslinked organic granular (organosilicon, granules of polystyrene etc.).From obtaining good smoothness, resistance to scraping This viewpoint considers, preferably include spherical silica particles, spherical alumina granule, crosslinked organic granular and it Composite particles, particularly preferably spherical organic silicon grain.Spherical organic silicon resin particle situation as granule B is being used Under, when and with polyphenylene oxide as aftermentioned thermoplasticity noncrystalline resin when, make thermostability especially high due to synergism.

The alignment films of the present invention comprise resin combination, and the polystyrene that this resin combination contains above-mentioned syndiotactic structure gathers Compound, mean diameter are 0.5 ~ 5.0 μm of porous particle and silicone oil, its be by by this resin combination along at least single shaft Direction, preferably biaxially oriented stretching, so that the alignment films of molecular chain orientation.

And, the resin combination of the present invention preferably comprises following thermoplasticity noncrystalline resin Y.Thermoplasticity amorphous referred to herein Resin Y is preferably, the heat being the Tg higher than SPS using the glass transition temperature Tg that DSC (differential scanning calorimetry (DSC)) obtains Plasticity noncrystalline resin.If coordinating this analog thermoplastic noncrystalline resin Y in SPS, serve not only as the glass transition of mixture Temperature Tg improves, and thermostability improves, and the dielectric breakdown voltage under high temperature also improves.In addition, the hot chi of alignment films also can be made Very little have good stability, draftability also improves.From this viewpoint, the glass transition temperature Tg of thermoplasticity noncrystalline resin Y is preferred For more than 150 DEG C, more preferably more than 180 DEG C, particularly preferably more than 200 DEG C.Thermoplasticity noncrystalline resin Y joined together Glass transition temperature Tg higher, the raising effect of the effect above such as thermal dimensional stability is bigger.If squeezing in view of melting Go out, then the upper limit of essence is preferably 350 DEG C, more preferably 300 DEG C.

As this analog thermoplastic noncrystalline resin Y, preferably it is exemplified as the aromatic polyethers such as polyphenylene oxide, Polyetherimide, gathers Carbonic ester, polyarylate, polysulfones, polyether sulfone, polyimides etc..Wherein, polyphenylene oxide is due to easily making draftability improve and and antioxygen During agent combination, there is synergism, or because so that thermostability, dimensional stability is improved but also dielectric breakdown voltage Improve further, therefore particularly preferably.As polyphenylene oxide resin used herein, can enumerate and have known resin, for example：Poly- (2,3- dimethyl -6- ethyl -1,4- phenylate (phenylene ether)), poly- (2- methyl -6- chloromethyl -1,4- phenylate), poly- (2- methyl -6- ethoxy -1,4- phenylate), poly- (2- methyl -6- normal-butyl -1,4- phenylate), poly- (2- ethyl -6- isopropyl -1, 4- phenylate), poly- (2- ethyl -6- n-pro-pyl -1,4- phenylate), poly- (2,3,6- trimethyl -1,4- phenylate), poly- (2- (4 '-methyl Phenyl) -1,4- phenylate), poly- (2- bromo- 6- phenyl -1,4- phenylate), poly- (2- methyl -6- phenyl -1,4- phenylate), poly- (2- benzene Base -1,4- phenylate), poly- (2- chloro- 1,4- phenylate), poly- (2- methyl isophthalic acid, 4- phenylate), poly- (2- chloro- 6- ethyl -1,4- phenylate), Poly- (the chloro- 6- of 2- bromo- 1,4- phenylate), poly- (2,6- diη-propyl -1,4- phenylate), poly- (2- methyl -6- isopropyl -1,4- benzene Ether), poly- (2- chloro- 6- methyl isophthalic acid, 4- phenylate), poly- (2- methyl -6- ethyl -1,4- phenylate), poly- (the bromo- 1,4- benzene of 2,6- bis- Ether), poly- (the chloro- 1,4- phenylate of 2,6- bis-), poly- (2,6- diethyl -1,4- phenylate), poly- (2,6- dimethyl -1,4- phenylate) etc. all Polymers and their copolymer.In addition, also suitably using these resins after the modifier modifications such as maleic anhydride, fumaric acid Modifier.And then, can also use the vinyl aromatic compounds such as styrene and above-mentioned polyphenylene oxide graft copolymerization or embedding The copolymer of Duan Gongju.Wherein, particularly preferably poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylate).

For the intrinsic viscosity of polyphenylene oxide resin, when measuring in chloroform, at 30 DEG C, the preferably model of 0.2 ~ 0.8dl/g Enclose, be more preferably the scope of 0.3 ~ 0.6dl/g.When intrinsic viscosity is less than 0.2dl/g, the machinery of gained resin combination is strong sometimes Degree reduces.When on the other hand, more than 0.8dl/g, there is the mobility reduction of gained resin combination, melt-shaping is thin film etc. When processing become difficult trend.Polyphenylene oxide resin can be used in combination two or more, now can be by polyphenylene oxide trees different for intrinsic viscosity Fat mixes and reaches required intrinsic viscosity.

The alignment films of the present invention, preferably with respect to the quality of this alignment films, coordinate below more than 5 mass % and 48 mass % Above-mentioned thermoplasticity noncrystalline resin Y.By thermoplasticity noncrystalline resin Y is coordinated with the amount of above range, excellent heat resistance can be made, and Increase the raising effect of dielectric breakdown voltage.I.e., it is possible to the dielectric breakdown voltage under raising high temperature.In the case that content is very few, Thermostability has the trend of variation, and the raising effect of dielectric breakdown voltage has the trend of reduction, the raising effect of draftability Not.From this viewpoint, the content of thermoplasticity noncrystalline resin Y is more preferably more than 8 mass %, more preferably 11 mass % Above, it is particularly preferably more than 20 mass %.In addition, in the case that content is excessive, the crystallinity of SPS has the trend of reduction, thin film Thermostability have the trend of variation.From this viewpoint, the content of thermoplasticity noncrystalline resin Y is more preferably below 45 mass %, enters One step is preferably below 40 mass %, is particularly preferably below 35 mass %.

Certainly, in the range of the without prejudice to purpose of the present invention, the alignment films of the present invention are except containing above-mentioned SPS, thermoplastic Beyond property noncrystalline resin Y, can also further and use other resins.

<Antioxidant>

The alignment films of the present invention preferably comprise antioxidant.As antioxidant, can be to catch the free radical generating and prevent The main anti-oxidant of the oxidation or peroxide generating is decomposed and any one in the auxiliary antioxidant of anti-oxidation.Make Phenol antioxidant, amine system antioxidant can be included for main anti-oxidant, phosphorus system antioxygen can be included as auxiliary antioxidant Agent, sulfur system antioxidant.Wherein preferred main anti-oxidant, particularly preferred phenol antioxidant.

In addition, antioxidant preferably its pyrolysis temperature is more than 250 DEG C.If pyrolysis temperature is high, the medium under high temperature The raising effect of breakdown voltage increases.In the case that pyrolysis temperature is too low, when melt extruding, antioxidant is pyrolyzed in itself, deposits Trend the problems such as easy generation pollution operation, polymer coloration are yellow, not preferably.From this viewpoint, antioxidant More preferably more than 280 DEG C of pyrolysis temperature, more preferably more than 300 DEG C, be particularly preferably more than 320 DEG C.The present invention Antioxidant be preferably difficult the antioxidant that is pyrolyzed although the preferably high antioxidant of pyrolysis temperature, but actually its The upper limit is less than 500 DEG C about.

Additionally, it is preferred that the fusing point of antioxidant is more than 90 DEG C.In the case that fusing point is too low, the antioxidation when melt extruding Agent is faster melted than polymer, there is the trend of the screw feed partial slip in extruder for the polymer.Thus, make polymer Supply unstable, produce thin film uneven thickness (thick body speckle) be deteriorated the problems such as.From this viewpoint, the fusing point of antioxidant is more It is preferably more than 120 DEG C, more preferably more than 150 DEG C, particularly preferably more than 200 DEG C.On the other hand, antioxidant In the case that fusing point is too high, when melt extruding, antioxidant is difficult to melt, and there is the trend that the dispersion in polymer is deteriorated.By This, the additive effect producing antioxidant is only the problems such as local occurs.From this viewpoint, the fusing point of antioxidant is preferably Less than 300 DEG C, more preferably less than 250 DEG C, more preferably less than 220 DEG C, particularly preferably less than 170 DEG C.

As antioxidant as above, can also be directly using commercially available product.As commercially available product, for example, preferably enumerate Go out：Tetramethylolmethane four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester] (Ciba Specialty Chemicals company System：Trade name IRGANOX1010), N, N '-bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propiono] hydrazine (Ciba Specialty Chemicals company system：Trade name IRGANOX1024), N, double [3- (3,5- bis- uncle of N '-hexane -1,6- diyl Butyl -4- hydroxy phenyl) propionic acid amide .] (Ciba Specialty Chemicals company system：Trade name IRGANOX1098) etc..

On the basis of the quality of alignment films, the content of antioxidant is preferably below more than 0.1 mass % and 5 mass %.Logical Cross and antioxidant is contained with the content of above-mentioned numerical range, the raising effect of dielectric breakdown voltage can be increased.Antioxidant In the case that content is very few, the additive effect that there is antioxidant is insufficient, dielectric breakdown voltage raising effect reduces becomes Gesture.More than this viewpoint, content more preferably 0.2 mass % of antioxidant, more than more preferably 0.5 mass %, More than particularly preferably 0.7 mass %.On the other hand, in the case that content is excessive, in biaxially-stretched film, antioxidant has easy coagulation Trend, had the trend of increase by the defect that antioxidant causes, the raising effect of dielectric breakdown voltage made due to this defect Decline.From this viewpoint, the content of antioxidant is more preferably below 3 mass %, is more preferably below 2 mass %, spy You Xuanwei not be below 1.5 mass %.

These antioxidants can be used alone one kind it is also possible to be used in combination two or more.

<Other additives>

In the range of the without prejudice to purpose of the present invention, such as in order to improve formability, mechanics physical property, superficiality etc. further, The alignment films of the present invention can contain other resinous principles different from thermoplasticity noncrystalline resin Y, or add antistatic additive, The additives such as toner, weather resisting agent.As long as in addition, in the range of the without prejudice to purpose of the present invention, can also on a small quantity and use porous Inert particle beyond granule and above-mentioned granule B.

<Metal level>

The alignment films of the present invention are by making capacitor in for example, at least one side superimposed layer metal level.Material for metal level Matter, is not particularly limited, for example, can include aluminum, zinc, nickel, chromium, stannum, copper and their alloy.And then, these metal levels Can be aoxidized in right amount.In addition, in order to be simply forming metal level, metal level is preferably the evaporation type adopting vapour deposition method to be formed Metal level.

In addition, when lamination is carried out to metal level, by metal is arranged further on the surface of the coating layer of the present invention Layer, can make substrate layer and metal level have the bonding force of appropriateness, implement gold during the processing such as winding in the manufacture of thin film capacitor Belong to layer will not peel off, play the function as capacitor.And then, make coating layer and metal level have appropriate cohesive, that is, simultaneously Make to discharge, be also that the little coating layer of surface energy is first peeled off from thin film, only metal level and coating layer are destroyed, and thin film is not Destroyed, the raising effect of dielectric breakdown voltage thus without causing short-circuit condition, can be increased.

<Film characteristics>

(refractive index of thickness direction)

The refractive index in the alignment films preferred thickness direction of the present invention is more than 1.575 and less than 1.635.By making thickness direction Refractive index reaches above-mentioned numerical range, can improve dielectric breakdown voltage further.In addition, film breaks in thin film fabrication operation Frequency reduce it is easy to improve production efficiency.From this viewpoint, the refractive index of thickness direction is preferably less than 1.620, enters one Step is preferably less than 1.615, particularly preferably less than 1.610.On the other hand, in the case that the refractive index of thickness direction is too low, Dielectric breakdown voltage has the trend of reduction.

In addition, the frequency of high-insulativity thin film film breaks in the manufacturing process of capacitor of the present invention increases, electric capacity The production efficiency of device is easily reduced.And then, the trend of uneven thickness variation that there is thin film is it is difficult to obtain the electric capacity of stay in grade Device.From this viewpoint, the refractive index of thickness direction is preferably more than 1.590, more preferably more than 1.595, especially excellent Elect more than 1.600 as.

The refractive index of above-mentioned thickness direction can be adjusted by the stretching condition of thin film.

(film thickness)

The thickness of the alignment films of the present invention is not particularly limited, from the aspect of the more thin effect present invention more easily, special Not You Xuanwei 0.4 μm less than 6.5 μm.More preferably 0.4 μm less than 6.0 μm, particularly preferably 0.5 μm Less than 3.5 μm.In addition, by reaching above-mentioned film thickness, the high capacitor of electrostatic capacitance can be obtained.

(voidage)

The alignment films of the present invention do not contain space preferably on the surrounding parenchyma of porous particle.Being substantially free of space in the present invention is Refer to, without space, or containing the space of degree that will not cause particle detachment or containing dielectric breakdown voltage will not be made to reduce Degree space.Refer to when measuring aftermentioned voidage, voidage is less than 50%, is particularly preferably less than 30%.Should Illustrate, if voidage exceedes the upper limit, not only work in-process can cause filler to come off, pollute operation, and surface roughness Change, the winding producing film rolling is bad.

(dielectric breakdown voltage (BDV))

Dielectric breakdown voltage (BDV) at 120 DEG C for the alignment films of the preferred present invention is more than 450kV/mm.Dielectric breakdown voltage Even if representing that also there is excellent dielectric breakdown voltage at high temperature in above-mentioned numerical range.This dielectric breakdown voltage is more preferably For more than 500kV/mm, more preferably more than 520kV/mm.

In addition, the alignment films of the present invention are for the deviation of dielectric breakdown voltage, its standard deviation be preferably 40kV/mm with Under, more preferably below 30kV/mm, more preferably below 20kV/mm.

The alignment films of the present invention by using specific porous particle, can increase dielectric breakdown voltage meansigma methodss and And reduce its standard deviation, it is possible to increase reliability of material during electrically insulating material as capacitor etc..That is, due to subtracting The standard deviation of little dielectric breakdown voltage, therefore can suppress the reduction of dielectric breakdown voltage minima, increase dielectric breakdown voltage Meansigma methodss.

<The manufacture method of thin film>

The method that the alignment films of the present invention substantially can be accumulated using existing known or this area is obtaining.Hereinafter, right Manufacture method for obtaining the alignment films of the present invention is described in detail.Should illustrate, the alignment films of the present invention can be uniaxial orientation Film is alternatively Biaxially oriented film, from the aspect of production efficiency, the balance of physical property, preferably Biaxially oriented film.Hereinafter, with twin shaft Illustrate as a example alignment films.

First, as described above, the resin combination being combined with SPS, porous particle and silicone oil is carried out heating melting, make Non-stretched.Specifically, in fusing point (Tm, the unit of resin combination：DEG C) more than and (Tm+50 DEG C) below at a temperature of enter Row heating melting, extrudes slabbing, and cooling and solidifying obtains non-stretched.The intrinsic viscosity that gained is non-stretched be preferably 0.35 ~ The scope of 0.9dl/g.

Then, this non-stretched is carried out biaxial stretch-formed.Stretching can be to longitudinally (mechanical direction of principal axis) with laterally (with machinery The direction of principal axis direction vertical with thickness direction) stretch it is also possible to stretch successively in any order simultaneously.The feelings for example stretching successively Under condition, first along single shaft direction, in (glass transition temperature (Tg, the unit of resin combination：DEG C) -10 DEG C) more than and (Tg+ 70 DEG C) below at a temperature of, with more than 3.2 times and less than 5.8 times, be preferably more than 3.3 times and less than 5.4 times, excellent further The multiplying power electing more than 3.4 times and less than 5.0 times as is stretched, then along the direction orthogonal with this single shaft direction, in more than Tg And (Tg+80 DEG C) below at a temperature of, with more than 3.8 times and less than 5.9 times, be preferably more than 4.0 times and less than 5.5 times, more It is preferably more than 4.1 times and less than 5.1 times, be more preferably that more than 4.2 times and less than 4.9 times of multiplying power is stretched.Enter And, area stretch multiplying power (=vertical stretching ratio × horizontal stretching ratio) is more than 12.0 times of situation, can obtain possessing above-mentioned putting down The thin film of surface orientation coefficient, therefore preferably.If area stretch multiplying power reduces, thermostability is deteriorated, not preferably.Therefore, area draws Stretch more preferably more than 13.0 times of multiplying power, be more preferably more than 13.5 times, particularly preferably more than 14.0 times.In addition, such as Fruit area stretch multiplying power is too high, then easily rupture, not preferably when masking, stretching.From this viewpoint, area stretch multiplying power is excellent Elect less than 22 times, more preferably less than 20 times, more preferably less than 18 times, particularly preferably less than 17 times as.

Should illustrate, in the present invention, can pass through on non-stretched or this non-stretched preferably edge is longitudinally being entered Masking liquid for forming coating layer is coated with the monadic stretching membrane of row uniaxial tension, thus forming coating layer.

Then, carry out heat fixation at a temperature of (Tg+70 DEG C) ~ Tm.The temperature of heat fixation is more than 200 DEG C and 260 DEG C Below, it is preferably more than 225 DEG C and less than 255 DEG C, more preferably more than 235 DEG C and less than 250 DEG C.Heat-fixing temperature mistake In the case of height, especially in the relatively thin thin film of manufacture film thickness, easily there are film breaks, and uneven thickness is deteriorated.As After fruit heat fixation as needed lower 20 DEG C than heat-fixing temperature ~ 90 DEG C at a temperature of carry out relaxation processes, then dimensional stability Improve.

Then, the stretched film of second present invention is illustrated.

<Stretched film>

The stretched film of second present invention comprises resin combination, and this resin combination contains the polystyrene resin of syndiotactic structure (hereinafter sometimes referred to SPS) and mean diameter A are 0.5 ~ 5.0 μm of porous silica silicon grain.

For the polystyrene resin of syndiotactic structure used herein, can carry out and first present invention in illustrate between advise The same explanation of the polystyrene resin of structure.

Below unless stated otherwise, for the porous silica silicon grain contained by the stretched film of the present invention, can carry out with upper State the same explanation of the porous silica silicon grain of explanation in first present invention.Should illustrate, different from first present invention, Possess specific specific surface area and DBA value in two present invention, therefore and silicone oil can not be used.

Porous silica silicon grain further requirement DBA value (di-n-butyl amine adsorbance) used in second present invention is 200 mMs/below kg, preferably 100 mMs/below kg.In the case that DBA value is more than 200 mMs/kg, not only many Dispersion in resin combination for the hole silica dioxide granule is deteriorated, and is configured to be also easy to produce between resin and granule during stretched film Space, it is not preferable.Should illustrate, DBA value described herein is to process porous silica with the toluene solution of di-n-butyl amine Di-n-butyl amine adsorbance (with respect to the adsorbance (mM) of the di-n-butyl amine of 1kg granule) during silicon grain.

The manufacture method of this porous silica silicon grain is not particularly limited, and can be readily derived in the following manner： For the surface of the porous silica silicon grain being manufactured using the existing known method such as sol-gal process, sedimentation method, using example As alkylalkoxysilane compounds, silicon nitrogen silane compound etc. are processed, and the silanol group of particle surface is modified, Thus obtain.In the case that particle surface silanol group is more, reduce with the affinity of the polystyrene resin of syndiotactic structure, And dispersibility in resin combination for the granule reduces.In addition, being not only configured to easily produce between resin and granule during stretched film Raw space, and the activity rising of particle surface, easily produce the drawbacks such as the coagulation again of granule when being matched with resin material.

In addition, porous silica silicon grain be preferably primary particle coagulation agglutinating particle, further preferably this one Secondary grain diameter be 0.01 ~ 0.1 μm, pore volume in the range of 0.5 ~ 2.0ml/g, in addition, average pore size is preferably in 5 ~ 25nm model In enclosing.Think by meeting this important document, due to being processed into stress during stretched film etc., this granule appropriateness deformation, make around granule The diameter in the space being formed reduces.

The stretched film of second present invention described above, in addition to containing above-mentioned porous silica silicon grain, preferably comprises Mean diameter A is 0.01 μm less than 0.5 μm of granule (hereinafter sometimes referred to inert particle C).By containing this inertia Granule C, can keep high dielectric breakdown voltage to make the smoothness of stretched film well, and can obtain windability excellent drawing Stretch film.In the case that mean diameter A of inert particle C is too small, the improvement of smoothness has the trend of reduction, windability improvement Effect also reduces.On the other hand, in the case of excessive, the low raised excessive height of film surface, lead to smoothness too high, from And it is also easy to produce the windability reductions such as end face skew in winding.In addition, there are the trend of increase, resistance to scraping, Jie in the space in thin film Matter breakdown voltage reduces.From this viewpoint, mean diameter A of inert particle C be preferably 0.05 μm less than 0.5 μm, More preferably 0.1 μm less than 0.5 μm, particularly preferably 0.2 ~ 0.4 μm.Should illustrate, preferably this inert particle C Mean diameter A be less than above-mentioned porous silica silicon grain mean diameter A, the difference between the two be preferably more than 0.2 μm.

This inert particle C preferable particle size ratio (major diameter/minor axis) is 1.0 ~ 1.3 spherical particle.Particle diameter is than further preferably For 1.0 ~ 1.2, particularly preferably 1.0 ~ 1.1.If particle diameter ratio is in above-mentioned numerical range, windability raising can be made to imitate The raising effect of fruit and dielectric breakdown voltage is bigger.

This inert particle can be any one in organic system granule, inorganic system granule.As organic system granule, for example, can arrange Enumerate：Polystyrene resin beads, silicone resin particles, acrylic resin particle, styrene-acrylic resins granule, two The high scores such as vinyl benzene-acrylic resin particle, polyester resin particle, polyimide resin granule, melamine resin particles Sub- resin particle.Wherein, from the viewpoint of smoothness and resistance to scraping are excellent, preferably silicone resin particles, polystyrene tree Fat granule, particularly preferred spherical organic silicon resin particle, spherical polystyrol resin particle as mentioned above.In addition, as inorganic It is granule, example (1) ~ (15) of the granule B of explanation in first present invention can be included.Wherein, excellent from smoothness and resistance to scraping From the viewpoint of different, preferably calcium carbonate granule, silica dioxide granule, particularly preferred silica dioxide granule.As described above, such nothing Machine system granule is preferably spherical, particularly preferred spherical silica particles.

As inert particle C most preferably spherical organic silicon resin particle.Spherical organic silicon resin particle conduct is used In the case of inert particle, and with polyphenylene oxide as aftermentioned thermoplasticity noncrystalline resin when, make thermostability by synergism Especially high.

Content in resin combination 100 mass % for this inert particle C is preferably 0.01 ~ 3 mass %, is more preferably 0.05 Below ~ 2 mass %, more preferably 0.1 ~ 0.5 mass %, particularly preferably 0.1 ~ 0.3 mass %.By within the above range Containing this inert particle, can keep high dielectric breakdown voltage and make thin film operability good.

Should illustrating, inert particle being added directly or as master batch chips (マ ス タ チ ッ プ) so that inciting somebody to action When resin combination melt-shaping without inert particle is thin film, the inert particle content in gained thin film is in above range Interior.

The stretched film of second present invention preferably also contains thermoplasticity noncrystalline resin.For thermoplasticity amorphous tree described herein Fat, can carry out the explanation same with the thermoplasticity noncrystalline resin of explanation in above-mentioned first present invention.

In addition, in the range of the without prejudice to purpose of the present invention, except containing above-mentioned in the stretched film of second present invention Beyond SPS, thermoplasticity noncrystalline resin, other resins also and can be used.

The stretched film of second present invention preferably also contains antioxidant.As antioxidant, can carry out and above-mentioned first The same explanation of the antioxidant of explanation in invention.

In the range of the without prejudice to purpose of the present invention, in order to improve such as Film making properties, mechanics physical property, superficiality further Stretched film Deng, second present invention can also contain other resinous principles different from thermoplasticity noncrystalline resin, or adds anti- The additives such as electrostatic agent, coloring agent, weather resisting agent.In addition, in the range of the without prejudice to purpose of the present invention, can also be used in combination on a small quantity Inert particle beyond above-mentioned granule.

For the stretched film of second present invention, greatest length present in refractive index for thickness direction and thin film Thick agglutinating particle for more than 25 μm, can carry out the explanation same with the content of explanation in above-mentioned first present invention.

The stretched film of second present invention does not contain space preferably on the surrounding parenchyma of porous silica silicon grain.Essence herein Upper identical with the implication of explanation in first present invention without space.Should illustrate, if voidage is more than 50%, not only add Can cause particle detachment, pollution operation in work, and surface roughness changes and produces the operability such as winding is bad of film rolling Reduce, in addition, dielectric breakdown voltage reduces and its deviation also easily increases (dielectric breakdown characteristic is easily reduced).

The thickness of the stretched film of second present invention is not particularly limited, in terms of the more thin effect present invention more easily Consider, particularly preferably 0.4 ~ 6.5 μm.More preferably 0.4 ~ 6.0 μm, particularly preferably 0.5 ~ 3.5 μm.On reaching State film thickness, the high capacitor of electrostatic capacitance can be obtained.

Dielectric breakdown voltage (BDV) at 120 DEG C for the stretched film of further preferred second present invention be 450V/ μm with On.Even if dielectric breakdown voltage meets this important document represents also there is excellent dielectric breakdown voltage at high temperature.This dielectric breakdown Voltage is more preferably more than 500V/ μm, more preferably more than 520V/ μm.

In addition, the standard deviation of above-mentioned dielectric breakdown voltage is preferably less than 40V/ μm, is more preferably less than 30V/ μm, enters One step is preferably less than 20V/ μm.This standard deviation meets above-mentioned important document and represents that the reduction of the dielectric breakdown voltage of local is little (partially Difference is little), the reliability of material during electrically insulating material as capacitor etc. can be improved.

For the stretched film of second present invention, the centerline average surface roughness Ra of preferably its at least one side is 7 ~ 89nm.By making centerline average surface roughness Ra within this range, windability raising effect can be increased.In addition, can So that resistance to blocking (blocking resistance) improves, the outward appearance of volume is good.Centerline average surface roughness Ra is too low In the case of, smoothness has too low trend, and windability raising effect reduces.On the other hand, in the case of too high, smoothness There is too high trend, during winding, easily cause end face skew etc., windability raising effect to reduce.From this viewpoint, center The lower limit of line average surface roughness Ra is more preferably more than 11nm, more preferably more than 21nm, particularly preferably 31nm More than.In addition, the upper limit of centerline average surface roughness Ra is more preferably below 79nm, more preferably below 69nm, Particularly preferably below 59nm.

In addition, for the stretched film of second present invention, 10 points of mean roughness Rz of preferably its at least one side are 200 ~ 3000nm.By making 10 points of mean roughness Rz within this range, windability raising effect can be increased.10 points of average roughness In the case that degree Rz is too low, rolling de-gas during rolling has the trend of reduction, the windability raising such as thin film easily slides laterally Effect reduces.Particularly, in the case that film thickness is relatively thin, the toughness (Off ィ Le system waist) of thin film disappears, therefore de-gas There is the trend reducing further, windability raising effect reduces further.On the other hand, 10 points of mean roughness Rz are too high In the case of, thick projection has the trend of increase, and the raising effect of dielectric breakdown voltage reduces.From this viewpoint, 10 points average The lower limit of roughness Rz is more preferably more than 600nm, more preferably more than 1000nm, particularly preferably more than 1250nm. In addition, the upper limit of 10 points of mean roughness Rz is more preferably below 2600nm, more preferably below 2250nm, particularly preferably For below 1950nm.

<The manufacture method of thin film>

The stretched film of second present invention described above, in addition to can be without silicone oil, can adopt and above-mentioned first present invention The manufacture method that the manufacture method of middle explanation is same is manufactured.

<Resin combination>

The resin combination preferably using in the manufacture of the stretched film of second present invention, is the polystyrene in above-mentioned syndiotactic structure It is the resin combination of melting mixing porous silica silicon grain in resin.

Mean diameter B of porous silica silicon grain used herein is preferably 0.5 ~ 5 μm, particularly preferably 0.8 ~ 3.0 μ The scope of m.In the case that this mean diameter is less than 0.5 μm, there is the porous silica that melt-shaping is in thin film during thin film etc. The mean diameter A reduction of silicon grain, not enough, windability, operability the is also insufficient trend of smoothness.On the other hand, more than 5 μm In the case of, when melt-shaping is thin film etc., because the diameter that stretching etc. easily makes the space being formed around granule increases.In addition, On the basis of resin combination amount of substance, the content of this granule is 0.01 ~ 10 mass %, the scope being preferably 0.5 ~ 5.0 mass %.If Content be then configured to thin film etc. less than 0.01 mass % after formed products smoothness not enough, operability is insufficient.On the other hand, In the case of 10 mass %, dispersion in resin combination for the granule is deteriorated, and it is not preferable.Should illustrate, by resin group The direct melt-shaping of compound and in the case of being configured to thin film etc., the content of granule as described above, it is preferred to for 0.01 ~ 3 mass %, The scope of more preferably 0.02 ~ 1 mass %, particularly preferably 0.05 ~ 0.5 mass %.On the other hand, with matrix resin etc. In the case that dilution carries out melted masking, using the resin combination of content height, for example, 0.5 ~ 10 mass %, it is diluted making The content being configured to (in thin film) in the resin combination of thin film etc. reaches above range.

And then, as mentioned above it is desirable to the DBA value of porous silica granule is 200 mMs/below kg, is preferably 100 MM/below kg.In the case that DBA value is more than 200 mMs/kg, not only porous silica silicon grain is in resin combination In dispersion be deteriorated, and be configured to be also easy to produce space between resin and granule during stretched film, it is not preferable.

In addition, as described above, the compression ratio of porous silica silicon grain is preferably 20 ~ 90%, particularly preferably 50 ~ 85% Scope.Think by making compression ratio within this range, due to being processed into stress during stretched film etc., this granule appropriateness deformation, make The diameter in the space being formed around granule reduces.

As described above, this resin combination preferably comprises thermoplasticity noncrystalline resin, particularly polyphenylene oxide resin.By resin The direct melt-shaping of compositionss and in the case of being configured to thin film etc., on the basis of the quality of resin combination, thermoplasticity amorphous The content ratio of resin is preferably below 48 mass %, the scope of more preferably 5 ~ 48 mass %.Thus, it is possible to make thermostability Excellent, and improve dielectric breakdown voltage, you can to obtain the stretched film of the raising of the dielectric breakdown voltage under high temperature.Content is very few In the case of, the raising effect of thermostability has the trend of reduction, and the raising effect of dielectric breakdown voltage also has becoming of reduction Gesture, the raising of draftability is not sufficiently effective.From this viewpoint, the content of thermoplasticity noncrystalline resin is more preferably more than 8 mass %, More than more preferably 11 mass %, more than particularly preferably 20 mass %.In addition, in the case that content is excessive, the crystallization of SPS Property have the trend of easy reduction, the thermostability of thin film also has the trend of reduction.From this viewpoint, the content of thermoplasticity noncrystalline resin Below more preferably 45 mass %, below more preferably 40 mass %, below particularly preferably 35 mass %.On the other hand, exist Resin combination is used as masterbatch (masterbatch), and without porous silica silicon grain, poly- containing such as syndiotactic structure In the case that the masterbatch of the matrix resins such as phenylethylene resin series or other additives carries out melting mixing and dilutes, using polyphenylene oxide The content ratio of resin is high, such as content is the resin combination of 20 ~ 80 mass %, is diluted making to be configured to the resin of thin film Content in compositionss reaches above range.

For the mixed method of above-mentioned porous silica silicon grain and resin material, need not be particularly limited to, can be in resin The polymerization stage of material adds, it would however also be possible to employ melting mixing method is added in the resin material by polymerization gained.For example, may be used So that this granular powder and resin material to be supplied from the same supply mouth of melting mixing machine and to carry out melting mixing, it would however also be possible to employ First in the melting mixing machines such as the twin-screw mixer extruder with steam vent, put into resin material, then this granule is added with powder body The method at the position having melted to this resin material.Wherein, preferably this granule is pre-mixed with resin granular material or toner Afterwards, it is supplied to the method in the twin-screw mixer extruder with steam vent.According to the method thus it is speculated that because this granule is attached to tree Fat granule material or the surface of toner, when therefore being pulverized inside kneading machine, this granule is minimum with the contact interval of resin, So dispersibility improves further.

As the twin-screw mixer extruder with steam vent, preferably use following device：The interpolation mouth of granule is arranged on joins It is placed in the full thread portion of the screw rod within the twin-screw mixer extruder with steam vent, from above-mentioned interpolation opening's edge screw rod axle center side Downstream it is provided with the rotor segment having for making granule knead scattered feeding blade and return blade at least the one of side. Herein, gas exhaust piping is used for removing the by-product from resin.In addition, the twin-screw mixer extruder with steam vent preferably 1 ~ There is rotor segment at 3.If scraper plate without spin, the mixing dispersion of this granule reduces, if rotor segment more than 3 at; resin Propulsive force reduces and easily bends.Additionally, it is preferred that having the scattered kneading disk of mixing for supplementing this porous particle.

<Capacitor>

The stretched film of the invention described above can be by obtaining capacitor in for example, at least one side lamination metal layer.For metal level Material, be not particularly limited, for example, can include aluminum, zinc, nickel, chromium, stannum, copper and their alloy.And then, these gold Belong to layer can be aoxidized in right amount.In addition, in order to be simply forming metal level, metal level is preferably the steaming adopting vapour deposition method to be formed Plating type metal level.Should illustrate, when lamination is carried out to metal level, by pre-setting coating layer, stretch film layers (base can be made Material layer) and metal level have appropriateness bonding force, in the manufacture of thin film capacitor implement be wound around etc. processing when metal level will not Peel off, play the function as capacitor.Make coating layer and metal level have appropriate cohesive simultaneously, even if discharging, It is that the little coating layer of surface energy is first peeled off from thin film, only metal level and coating layer are destroyed, and thin film is not destroyed, thus not Short-circuit condition can be caused, the raising effect of dielectric breakdown voltage can be increased.

Embodiment

Hereinafter, by embodiment, the present invention is further described.Should illustrate, each characteristic value is surveyed using following methods Fixed.

(1) film thickness

Using electronic gauge (trade name " K-312A type " that Anritsu (strain) makes), under pin pressure 30g, measure film thickness.

(2) mean diameter of granule

(2-1) mean diameter A

Mean diameter A in thin film is as follows：Carrying out process with plasma reactor to film surface makes granule expose, using gold Sputter equipment forms the gold thin film evaporation layer of thickness 200 ~ 300 on this surface.Then, using scanning electron microscope 10,000 Observed under 5000 times, using Japanese レ ギ ュ レ タ (strain) LUZEX processed (Le ゼ ッ Network ス) 500, for 110 Granule, obtains its area equivalent particle size (Di), by wherein measure 5 maximum area equivalent particle sizes (Di) and 5 minimum areas Several averages of their the area equivalent particle size (Di) after except equivalent particle size (Di) are as mean diameter A of granule.

(2-2) mean diameter B

Mean diameter B before being added in polymer is obtained in the following manner.That is, it is used ethanol as disperse medium, make Obtain mean diameter with Shimadzu Seisakusho Ltd. laser diffraction formula particle size distribution device SALD-2000J by volume distributed median standard B.

(3) compression ratio of granule

For porous particle before being added in polymer, using micro- compression test MCTM-200 of Shimadzu Seisakusho Ltd.'s system (maximum load Lotus 1gf, minimum load 0.2gf), under conditions of load load speed 0.0725gf/sec, prepare n=5 particle diameter with averagely Particle diameter identical granule, the compression ratio under measuring load 0.2gf, calculate its meansigma methods as the compression ratio of granule.

(4) porous particle, other granules, silicone oil, thermoplasticity noncrystalline resin Y, the content of antioxidant are respectively according to aftermentioned Method is measuring.

Porous particle, other granules：Selective dissolution resin and the solvent of insoluble granule, will be molten for the orientation membrane sample of gained Xie Hou, the centrifugation from resin by granule, using granule with respect to example weight ratio (weight %) as granule content.Separately Outward, in the case of containing other granules, respective content is obtained according to the presence ratio of each granule.

Silicone oil：Pass through¹H-NMR mensure,¹³C-NMR measures, and with integrating number of times 32 times, using cryoprobe, (high sensitivity is visited Pin) determine the composition of silicone oil and each component amount.

Thermoplasticity noncrystalline resin Y：Pass through¹H-NMR mensure,¹³C-NMR measure, determine thermoplasticity noncrystalline resin Y composition and Each component amount.

Antioxidant：Pass through¹H-NMR mensure,¹³C-NMR measures, and determines the composition of antioxidant and each component amount.Should Illustrate, in N, double [3- (3,5- di-tert-butyl-hydroxy phenyl) the propionic acid amide .] (registered trade mark of N '-hexane -1,6- diyl Irg1098 in the case of), to the peak intensity produced by hydrogen in the hydrocarbon chain between tert-butyl-hydroxy phenyl and amido link Degree is measured.Based on this NMR measurement result, when obtaining stabilizer with resin reaction, it is converted into the content of former stabilizer.In addition, It is not mixed with the stabilizer of polymer reaction and with the stabilizer of polymer reaction, even if being conceived to same hydrocarbon chain In the case of also detecting that multiple peak positions, content is obtained according to their aggregate value.

(5) masking draftability

Under conditions of each embodiment and comparative example, supply polymer to extruder, according to following standard, to by mould (ダ イ ス) and the thin film masking in the stretching film making process producing shape and thin film of volatile ingredient when being melt extruded Property is evaluated,

◎：No thick agglutinator etc. during polymer melt extrusion, film making process also no ruptures, and can be produced；

〇：During polymer melt extrusion, thick agglutinator occurs, but no rupture, can be produced；

△：During polymer melt extrusion, thick agglutinator occurs, fracture occurs once in a while it is impossible to carry out steady production；

×：During polymer melt extrusion, thick agglutinator is obvious, or frequent generation fracture is it is impossible to be produced.

(6) filter boosting

Using Japanese PALL company system H-250 (sintering (grain) type filter that 25 μm of mesh), the resin of small porous particle A will be comprised It is converted into output (kg)/filter area (cm²) when, in 300 DEG C of extrusion temperature, 5kg/cm²In the case of lower filtration, evaluate Filter differential pressures (the Δ P that initial pressure when having filtered 100kg begins to ramp up：Unit is MPa), enter according to following standard Row is evaluated,

◎：During polymer melt extrusion, filter no boosts, can stably extrusion resin；

〇：During polymer melt extrusion, filter temporarily boosts, but can stably extrusion resin；

△：During polymer melt extrusion, the pressure of filter slowly rises it is impossible to extrusion resin steadily in the long term；

×：During polymer melt extrusion, the pressure of filter steeply rises, and is unable to extrusion resin in the short time.

(7) refractive index of thickness direction

Using the Abbe refractometer with sodium D-line (589nm) as light source, measure the refractive index of thickness direction under 23 DEG C, 65%RH (Nz).The refractive index of thickness direction is higher to mean that strand is orientated along film surface direction.

(8) thick agglutinating particle number

For film sample, using universal projector, amplify 20 times using transillumination, to 1m²Contained in area have 25 μ The granule number of more than m greatest length is counted.

(9) voidage

With microtome, thin film through-thickness and width are cut off, for tangent plane, use (strain) Hitachi scanning electron to show Micro mirror S-4700 observes the porous silica silicon grain in thin film on tangent plane and the space around them under 20000 times, right In 10 granules, obtain the section of each granule and the diameter in the film surface direction of each circumgranular space section, according under Formula calculates the voidage of each granule；

Voidage=((circumgranular aperture diameter-particle diameter)/circumgranular aperture diameter) × 100

For 10 granules, as average void fraction, evaluate in thin film substantially has space also to the meansigma methodss calculating voidage It is substantially tight；

〇：Substantially tight (average void fraction is less than 30%)

△：Substantially tight (average void fraction is more than 30% and is less than 50%)

×：Substantially there is space (average void fraction is more than 50%).

(10) surface roughness (Ra and Rz)

Using non-contact 3-D roughmeter (little slope studies made, ET-30HK), with the semiconductor laser of wavelength 780nm, light The light contact pilotage of 1.6 μm of beam diameter, in measured length (Lx) 1mm, 2 μm of sampling interval, cuts size (cut-off) 0.25mm, thickness 10,000 times of degree direction enlargement ratio, 200 times of horizontal magnification multiplying power, number of scanning lines 100 (therefore, measured length Ly=of Y-direction The raised distribution of film surface is measured under conditions of 0.2mm).When representing this roughness curved surface with Z=f (x, y), will be by following formula institute The value obtaining is as centerline average surface roughness (Ra, the unit of thin film：nm).

[mathematical expression 1]

.

In addition, in the raised distribution of the film surface by above-mentioned Ra gained, from the higher position of peak (Hp) take 5 points and Take at 5 points from the lower of paddy (Hv), obtain mean roughness (Rz, units according to the following formula at 10 points of：nm).

[mathematical expression 2]

.

(11) windability

In the manufacturing process of thin film, thin film is rolled up the web-like of 6000m, root with the speed of 550mm width, 100m/ minute Roll the outward appearance of shape, volume according to it, evaluated according to following standard；

A：The overall even surface roughness of film surface, the winding form of volume is good

B：Due to the impact of the thick agglutinating particle in thin film, the pimple (projection that 1 less than 5 in the surface of volume Shape swells), substantially well

C：Thick agglutinator quantity in thin film is a lot, and more than 5 pimples (convex shape protuberance) in the surface of volume, and outward appearance is bad

D：There is the thin film end face skew of volume, winding form is bad.

(12) dielectric breakdown voltage (BDV) and deviation

Using the Biaxially oriented film (stretching membrane sample) of gained, according to the DC examination described in Japanese Industrial Standards' JIS specification C2151 Plate electrode method in testing, using Tokyo essence electricity Co. Ltd. system ITS-6003, is surveyed with the rate of rise of 0.1kV/sec Fixed, voltage when puncturing is measured as dielectric breakdown voltage.Mensure is carried out n=50 time, and meansigma methodss are dielectric breakdown electricity Pressure, standard deviation is the deviation of dielectric breakdown voltage.Should illustrate, measure and carry out under 25 DEG C of room temperature.

(13) resistance to scraping

Thin film is cut into along its length 1/2 inch of width, length 400mm, makes the thin film cutting using thin film nigration machine In rustless steel guide finger (surface roughness：Ra is 40nm) the upper distance two moving, coming and going 200mm with the translational speed 20mm/ second Secondary (90 ° of circumvolution angle, outlet side tension force 50g).After movement, with Hitachi's scanning electron microscope S-4700 under 100 times, right Observe the adhesion amount of granule in the film contacts portion of guide finger and the guide finger contact surface of thin film, sentenced according to following standard Fixed.The accumulation width of the granule of scraping is less, and resistance to scraping is more excellent,

〇：Less than 0.20mm

△：0.20mm is less than 0.50mm

×：More than 0.50mm.

(14) resistance to blocking

Thin film is cut into the square of length of side 100mm, by the film overlay cutting make gross thickness be more than 20 μm (monolithic thin film Thickness is using 1 when more than 20 μm), make aluminium foil each 1 laminated body clipping up and down with same size.With hot press pair This laminated body is thermally compressed.Crimping condition is 125 DEG C of pressed temperature, moulding pressure 5MPa, 30 minutes pressing times.Crimping Afterwards, 30 minutes heat treatments will be carried out at laminated body in an oven 150 DEG C, measure the stripping of the thin film of laminated body after cooling and aluminium foil From power.The mensure of peeling force uses cupping machine, is measured, according to mensure under conditions of draw speed 300mm/min Result according to following standard determination adhesive,

〇：Almost naturally peel off, or Average peel force is below 1.0mN/mm；

△：Focal adhesion, but Average peel force is more than 1.0mN/mm and is below 3.0mN/mm；

×：All adhesions, Average peel force is more than 3.0mN/mm.

(15) the DBA value (adsorbance of di-n-butyl amine) of porous silica silicon grain

Sample 250mg after being dried 2 hours at 105 DEG C of precision weighing, is added thereto to the 1/500N-DBA solution (oil of 50ml Ether solvents), place 2 hours at 20 DEG C.Add chloroform 5ml, crystal violet indicator 2 ~ 3 in its supernatant 25ml, use 1/ 100N- perchloric acid solution (acetic anhydride solvent) is titrated to purple and is changed into blue, and titration value now is as Aml.It is additionally carried out sky Test as Bml in vain, calculate DBA value according to the following formula,

DBA value (mM/kg)=80 (A-B) f

Wherein, f is the titer of 1/100N- perchloric acid solution

(with reference to R.Meyer;Kautschuku.Gummi.,7[8],180-182(1954)).

[embodiment 1]

(the silicone oil attachment of porous silica silicon grain is processed)

For porous silica silicon grain (mean diameter=2.7 μm, compression ratio=66%, pore volume=1.5ml/g, average pore size =10nm) 100 mass parts, with spraying silicone oil (SHIN-ETSU HANTOTAI's シ リ U Application system, wire dimethyl polysiloxane, the KF-96- of spraying 100CS) 1 mass parts, are then placed in being stirred in mixer.

(melting mixing of resin material and porous silica silicon grain is processed)

Make the twin-screw mixer with steam vent using Kobe Steel's (strain) at resin input port and 2 with vacuum vent holes to squeeze Go out to be provided with the feeding blade of rotor disk at 2 (rotor disk) on machine KTX-46 and return blade and then in rotor segment The downstream side in portion is configured with kneading disk, is configured with to have in the downstream side of kneading disk and reversely transmits full flight screw The equipment of resistance portion.By resin input port, using 30 mass parts as thermoplasticity noncrystalline resin Y poly- (2,6- dimethyl-Isosorbide-5-Nitrae- Phenylene) ether (intrinsic viscosity measuring in chloroform is 0.32dl/g, glass transition temperature is 210 DEG C), and 70 mass parts work Weight average molecular weight for polystyrene resin is 3.0 × 10⁵And use¹³C-NMR measures and observes almost completely syndiotactic structure Polystyrene, with respect to these resins add up to, the above-mentioned porous silica silicon grain being attached with silicone oil of 0.1 mass parts, 2 mass Part is as tetramethylolmethane four [3- (3,5- di-tert-butyl-hydroxy phenyl) the propionic ester] (Ciba of antioxidant (C1) Specialty Chemicals company system：Trade name IRGANOX1010,120 DEG C of fusing point, 335 DEG C of pyrolysis temperature) press above-mentioned ratio Example mixing dispersion forms mixture, this mixture is put into from resin input port with the feed speed of 35 mass parts/Hr, with machine barrel 270 DEG C of temperature, screw speed 250rpm melt extrude into bar (strand) shape by nib.Then, with cooling bath, resin is cooled down Afterwards, cut with pelleter, obtained major diameter about 4mm, minor axis about 4mm, the resin combination fragment of length about 3mm.

(maskings of alignment films)

The resin combination of gained is dried 7 hours at 120 DEG C, is then fed in extruder, is melted at 300 DEG C Melt, after die slot (die slit) extrusion, in the upper cooling and solidifying of curtain coating drum (casting drum) being cooled to 50 DEG C, make not Drawing sheet.

By this non-stretched, in 140 DEG C of lower edges, longitudinally (mechanical direction of principal axis) stretches 3.5 times, after being then directed into stenter, edge Laterally (direction vertical with mechanical direction of principal axis and thickness direction) stretches 4.5 times.Now, stretched portion is divided into 4 regions, Cross directional stretch speed is 5000%/minute.In addition, the temperature of cross directional stretch is also divided into 4 stages, the temperature of first stage is 126 DEG C, the temperature of terminal stage be 145 DEG C.Then, carry out 9 seconds heat fixations at 250 DEG C, and then be cooled to 180 DEG C of phase Between transversely carry out 2% relaxation processes, obtain Biaxially oriented film the wound into rolls of 2.5 μm of thickness.The characteristic of gained thin film is shown In table 1.

[embodiment 2 ~ 20, comparative example 1 ~ 7]

In addition to the record according to table 1 ~ 3 is changed, operation similarly to Example 1 is repeated.Embodiment gained takes It is shown in table 1 and 2 to the evaluation result of film, the evaluation result of comparative example gained alignment films is shown in Table 3.

[table 1]

.

[table 2]

.

[table 3]

.

Porous silica in table 1 ~ 3 refers to porous silica silicon grain, and spherical organic silicon refers to cross-linked silicone tree Fat granule, non-porous silicon dioxide refers to spherical silica particles.Irg1010 in table 1 refer to tetramethylolmethane four [3- (3, 5- di-tert-butyl-hydroxy phenyl) propionic ester] (Ciba Specialty Chemicals company system：Trade name IRGANOX1010), Irg1098 refers to N, and N '-bis- 3- (3 ' 5 '-di-t-butyl -4 '-hydroxy phenyl) propiono hexa-methylene two Amine (Ciba Specialty Chemicals company system：Trade name IRGANOX1098), Irg565 refers to double (the just pungent sulfur of 2,4- Base) -6- (4 '-hydroxyl -3,5- di-tert-butyl amido) -1,3,5- triazine (Ciba Specialty Chemicals company system： Trade name IRGANOX565).PPE in table 1 and 2 refers to that (measure in chloroform consolidates poly- (2,6- dimethyl -1,4- phenylene) ether Have viscosity to be 0.32dl/g, glass transition temperature be 210 DEG C), PC refer to bisphenol A polycarbonate (go out light petrochemistry system, Go out light Merlon A300, glass transition temperature is 145 DEG C).In addition, in mean diameter hurdle in thin film in table 3, "-※ " Refer to that the coagulation of granule is many, stop the mensure of mean diameter.

[synthesis example 1]

So that the sodium silicate aqueous solution of 22wt% is reacted with the aqueous sulfuric acid of 37wt% using mixing nozzle, obtain silicon dioxide water-soluble Glue.Silica hydrosol is carried out gelation in about 7 minutes, obtains silica hydrogel.Will be thick for this silica hydrogel After being crushed to diameter about 10mm, carry out 5 hours hydrothermal treatment consists under conditions of 90 DEG C, pH9.0, then wash.Then, carry out 1 operation, i.e. using vibrated fluidized bed (central chemical industry machine company system, trade name " vibrational fluidized bed device VUA-15 type "), by water Silica hydrogel after washing is dried 60 minutes, obtains the silicon dioxide being dried to water content 7%.Then, carry out the 2nd operation, That is, add water in the silicon dioxide being dried, be adjusted to the silicon dioxide of water content 37%.Then carry out the 3rd work Sequence, i.e. use vibra fluidized bed drying 2 hours again, obtain the gelation silicon dioxide of water content 1%.Using jet mill pair This dried silicon dioxide carries out pulverization process, and 00 part of the silica 1 of gained is added in vibrated fluidized bed, and lateral dominance is used Air after dehumidifying carries out vibratory liquefaction side 12 parts of n-octytriethoxysilane of spraying and carries out fluidisation mixing 30 minutes.Then, Put into rapidly 25 DEG C of keeping temperature, in the constant temperature and humidity cabinet of humidity 90%, keep the silicon dioxide after being surface-treated for 72 hours Powder body.Again, in order that silicon dioxide disperses and carries out pulverization process using jet mill.Gained silicon-dioxide powdery 1 is (many Hole silica dioxide granule 1) characteristic value be shown in Table 4.

[synthesis example 2,3,5]

In addition to changing jet mill condition and adjusting mean diameter, carry out the process same with synthesis example 1.Gained dioxy The characteristic value of SiClx powder body 2,3,5 is shown in Table 4.

[synthesis example 4]

In addition to changing added n-octytriethoxysilane amount, carry out the process same with synthesis example 1.Gained dioxy The characteristic value of SiClx powder body 4 is shown in Table 4.

[synthesis example 6]

In order to make small particle, after first time jet mill is processed, with distilled water, silicon dioxide is made 10% slurry, increase Plus the case of wet attrition operation of sand milling (DYNO-MILL, capacity 5L), in addition carry out the process same with synthesis example 1.Gained two The characteristic value of silica powder 6 is shown in Table 4.If this silicon-dioxide powdery mean diameter is too small to be 0.3 μm, pressure cannot be measured Shrinkage.

[synthesis example 7]

In addition to the unreal surface treatment applying n-octytriethoxysilane, carry out the process same with synthesis example 1.Gained The characteristic value of silicon-dioxide powdery 7 is shown in Table 4.

[reference example 1]

Make the twin-screw mixer with steam vent using Kobe Steel's (strain) at resin input port and 2 with vacuum vent holes to squeeze Go out and the feeding blade of rotor disk and return blade and then the downstream in rotor segment portion at 2 are provided with machine KTX-46 Side is configured with kneading disk, is configured with setting of the resistance portion with reverse transmission full flight screw in the downstream side of kneading disk Standby.Mix the Rhizoma Sparganii engineering plastic putting into 40 mass parts as polyphenylene oxide resin (hereinafter sometimes referred to simply as PPE) from resin input port Expect Iupiace PX-100L (Tg210 DEG C) processed, 55.8 mass parts as syndiotactic structure polystyrene resin (below sometimes Referred to as SPS) go out light emerging product XAREC 60ZC processed, 0.2 mass parts as antioxidant Ciba Specialty Chemicals company system IRGANOX 1010.

And then, add 4 mass parts as many from the mid portion (downstream part of kneading disk) of twin-screw mixer extruder The above-mentioned silicon-dioxide powdery 1 of hole silica dioxide granule, carries out mixing dispersion.Now, with mixture quantity delivered for 35 mass parts/ Hr, 270 DEG C of barrel zone temperature, screw speed 250rpm, are melt extruded into strips by nib.Then, with cooling bath, resin is cooled down Afterwards, cut with pelleter, obtained major diameter about 4mm, minor axis about 4mm, the resin combination fragment of length about 3mm.Gained Resin combination fragment is shown in Table 4.

[reference example 2 ~ 5, reference comparative example 1 ~ 3]

Porous silica silicon grain used, the use ratio of PPE, SPS according to the record of table 3, in addition with reference example 1 with Sample obtains resin combination fragment.It is shown in Table 4 in the lump.

[reference example 6]

In addition to porous silica silicon grain, spherical organic silicon resin particle 4 mass the use of mean diameter B being also 0.3 μm Part, the use ratio of SPS, according to the record of table 1, is in addition similarly obtained resin combination fragment with reference example 1.Show in the lump In table 4.

[with reference to comparative example 4]

The spherical silica particles the use of mean diameter B being 2.0 μm (non-porous) are replacing porous silica used Grain, is in addition similarly obtained resin combination fragment with reference example 1.It is shown in Table 4 in the lump.

[table 4]

.

[embodiment 21]

By the resin combination fragment (master batch chips A) of gained, polyphenylene oxide resin (Mitsubishi Engineering-Plastics system in reference example 1 Iupiace PX-100L), the polystyrene resin (going out light emerging product XAREC 60ZC processed) of syndiotactic structure, in polyphenylene oxide resin 5 weight % Ciba Specialty are contained as antioxidant in (Mitsubishi Engineering-Plastics Iupiace PX-100L) After the master batch chips of Chemicals company system IRGANOX 1010 are separately dried, to obtain the ratio of the thin film of the described composition of table 5 Their mixing are supplied in extruder example, are melted at 300 DEG C, after die slot extrusion, rouse in the curtain coating being cooled to 50 DEG C On cooled and solidified, make non-stretched.Should illustrate, due to antioxidant, in the middle part of the film-forming process of thin film, swarming dissipates, Therefore the oxidation preventive content in raw mixture is adjusted to slightly volume, so that antioxidant content in the film reaches 1 weight Amount %.

By this non-stretched, in 140 DEG C of lower edges, longitudinally (mechanical direction of principal axis) stretches 3.5 times, after being then directed into stenter, edge Laterally (direction vertical with mechanical direction of principal axis and thickness direction) stretches 4.5 times.Now, horizontal draw speed be 5000%/point Clock, the temperature of cross directional stretch is divided into 4 stages, and the temperature of first stage is 126 DEG C, the temperature of terminal stage is 145 DEG C.So Afterwards, carry out 9 seconds heat fixations at 250 DEG C, and then transversely carry out 2% relaxation processes in the period being cooled to 180 DEG C, obtain thickness The Biaxially oriented film of 2.5 μm of degree wound into rolls.The characteristic of gained thin film is shown in Table 4.

[embodiment 22 ~ 24,26,29,30,33 ~ 37, comparative example 8 ~ 10,12,13]

Using the master batch chips as described in table 5 ~ 7, by polyphenylene oxide resin, polycarbonate resin, syndiotactic structure polystyrene Be resin and be used in combination containing the master batch chips of antioxidant so that gained thin film consist of shown in the record of table 5 ~ 7, except this Outside repeat similarly to Example 21 operation.The evaluation result of gained stretched film is shown in table 5 ~ 7.Should illustrate, real Apply in example 25,26, as the master batch chips containing antioxidant, using the syndiotactic structure containing 5 weight % IRGANOX 1010 Polystyrene resin (goes out light emerging product XAREC 60ZC processed).

[embodiment 25,27,28,31,32, comparative example 11]

By polyphenylene oxide resin, the polystyrene resin of syndiotactic structure, porous silica silicon grain and antioxidant and reference Example 1 is equally mixed, so that the composition of gained thin film is as shown in the record of table 5 ~ 7, obtains resin combination fragment first.Will Gained resin combination is dried, and is filmed similarly to Example 21 and obtains biaxially-stretched film.The evaluation result of gained stretched film It is shown in table 5 ~ 7.

[table 5]

.

[table 6]

.

[table 7]

.

PC in table 5 ~ 7 is that bisphenol A polycarbonate (goes out that light petrochemistry makes light Merlon A300, vitrification turns Temperature is 145 DEG C).

In addition, the Irg1010 in table 5 ~ 7 refers to tetramethylolmethane four [3- (3,5- di-tert-butyl-hydroxy phenyl) propanoic acid Ester] (Ciba Specialty Chemicals company system：Trade name IRGANOX1010), Irg1098 refers to N, N '-bis- 3- (3 ' 5 '-di-t-butyl -4 '-hydroxy phenyl) propiono hexamethylene diamine (Ciba Specialty Chemicals company system：Business Name of an article IRGANOX1098), Irg565 refers to double (just pungent the sulfenyl) -6- (4 '-hydroxyl -3,5- di-tert-butyl amido) -1 of 2,4-, 3,5- triazine (Ciba Specialty Chemicals company system：Trade name IRGANOX565).

Industrial applicability

For the alignment films of first present invention, resistance to scraping and windability excellent, therefore can be especially suitable for use as thin film capacitor and use Basement membrane.

In addition, for the stretched film of second present invention, the dispersibility of granule is excellent, and the aperture diameter being produced by granule Little, therefore resistance to scraping, operability, dielectric breakdown characteristic (dielectric breakdown voltage and its deviation) are excellent, may be particularly useful for thin film Capacitor is used.

Claims (13)

1. it is characterised in that this stretched film comprises resin combination, this resin combination contains the benzene second of syndiotactic structure to stretched film Alkene based polymer and mean diameter are 0.5 ~ 5.0 μm of porous particle, on the basis of the quality of this resin combination, porous particle Content be below more than 0.01 mass % and 3 mass % scope,

Described stretched film meets any one of following (1) or (2)：

(1) resin combination contains silicone oil, and on the basis of the quality of this porous particle, the content of silicone oil is the model of 0.1 ~ 3 mass % Enclose；Or

(2) porous particle be mean diameter A be 0.5 ~ 5 μm, the porous silica for 200 mMs/below kg for the DBA value Grain.

2. stretched film according to claim 1, this stretched film comprises resin combination, and between this resin combination contains, rule are tied The styrenic of structure, mean diameter are 0.5 ~ 5.0 μm of porous particle and silicone oil,

On the basis of the quality of this resin combination, the content of porous particle is the model of below more than 0.01 mass % and 3 mass % Enclose,

On the basis of the quality of this porous particle, the content of silicone oil is the scope of 0.1 ~ 3 mass %.

3. stretched film according to claim 1, this stretched film comprises resin combination, and between this resin combination contains, rule are tied The polystyrene resin of structure and mean diameter A are 0.5 ~ 5 μm, the porous silica for 200 mMs/below kg for the DBA value Silicon grain,

On the basis of resin combination amount of substance, the content of this porous silica silicon grain is 0.01 ~ 3 mass %.

4. stretched film according to any one of claim 1 to 3, wherein, resin combination contains thermoplasticity noncrystalline resin.

5. stretched film according to any one of claim 1 to 3, wherein, with respect to the quality of thin film, containing 5 mass % with Thermoplasticity noncrystalline resin below upper and 48 mass %.

6. stretched film according to any one of claim 1 to 3, wherein, the refractive index of thickness direction be more than 1.575 and 1.635 it is following.

7. stretched film according to any one of claim 1 to 3, wherein, with respect to the quality of thin film, containing 0.1 mass % Antioxidant above and below 5 mass %.

8. stretched film according to any one of claim 1 to 3, wherein, the pyrolysis temperature of described antioxidant is 250 DEG C More than.

9. stretched film according to any one of claim 1 to 3, wherein, porous particle or porous silica silicon grain Compression ratio is 20 ~ 90% scope.

10. stretched film according to any one of claim 1 to 3, wherein, described stretched film is with more than 0.01 mass % and 3 It is 0.01 μm less than 0.5 μm of granule that scope below quality % contains mean diameter.

11. stretched film according to any one of claim 1 to 3, wherein, more than 25 μm of contained greatest length in thin film Thick agglutinating particle quantity be 10/m²Below.

12. stretched film according to any one of claim 1 to 3, wherein, this contained porous particle or porous in thin film The voidage that the produced following formula of the surrounding of silica dioxide granule (1) represents is less than 50%：

Voidage=((circumgranular aperture diameter-particle diameter)/circumgranular aperture diameter) × 100 (1)

(1) voidage=((circumgranular aperture diameter-particle diameter)/circumgranular aperture diameter) × 100.

13. stretched film according to any one of claim 1 to 3, it is used for capacitor.