CN106459448B - Stretched film - Google Patents

Abstract

The present invention provides the alignment films of the windability and excellent styrene-based resin of resistance to scraping or particle dispersion is excellent, operability, resistance to scraping, dielectric breakdown excellent, the stretched film particularly suitable for thin film capacitor such as windability.I.e., stretched film is provided, the stretched film includes resin combination, the porous particle that the resin combination contains the styrenic of syndiotactic structure and average grain diameter is 0.5 ~ 5.0 μm, on the basis of the quality of the resin combination, the content of porous particle is 0.01 mass % or more and 3 mass % ranges below, the stretched film meets any one of following (1) or (2): (1) resin combination contains silicone oil, on the basis of the quality of the porous particle, the content of silicone oil is the range of 0.1 ~ 3 mass %；Or (2) porous particle be average grain diameter A be 0.5 ~ 5 μm, DBA value is 200 mMs/kg porous silica silicon particle below.

Description

Stretched film

Technical field

First the present invention relates to comprising rule (syndiotactic) structure styrenic an alignment films, into one Step specifically, is related to the stretched film for the styrenic comprising syndiotactic structure that windability and scratch is improved.

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

Background technique

In the past, thin film capacitor manufactured by the following method: by biaxial orientation polyethylene glycol terephthalate's film, double The metallic films such as the films such as axis oriented polypropylene films and aluminium foil are Chong Die, and are wound or the method for lamination.In recent years, with The requirement of circuit or electronic circuit miniaturization, the miniaturization of thin film capacitor, assemblingization also developing, in addition to electrical characteristic with It is outer also to require heat resistance in turn.In addition, not only using in driver's cabin in mobile applications, use scope, which is also extend to, starts In machine room, other than electrical characteristic, the thin film capacitor for the environment being suitble under high humidity at higher temperature is also required.

For above-mentioned requirements, Japanese Unexamined Patent Publication H02-143851 bulletin, Japanese Unexamined Patent Publication H03-124750 bulletin, Japan are special It opens H05-200858 bulletin, propose using heat resistance and electrical characteristic in No. 2008/156210 pamphlet of International Publication No. The method of excellent styrene-based film.But difficulty is film-made compared with the polyester film used in the past, and film It is easy to crack, therefore also require treatability when improveing manufacture capacitor.As such improvement film formation property, the method for treatability, lead to Often cooperate powder stuffing into resin, but conventionally used powder stuffing is when being made film for styrene-based resin, It is difficult to take into account windability and resistance to scraping.

In addition, being directed to above-mentioned requirements, proposed in Japanese Unexamined Patent Publication 2000-173855 bulletin using heat resistance than poly- to benzene Naphthalate film or the superior poly- 2,6-naphthalenedicarboxylic acid glycol ester film of polypropylene film, control its crystalloid State, inherent viscosity etc. are come the method that improves electrical characteristic.But since poly- 2,6-naphthalenedicarboxylic acid glycol ester is polar polymeric Object, therefore the improvement of electrical characteristic is limited.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication H02-143851 bulletin

Patent document 2: Japanese Unexamined Patent Publication H03-124750 bulletin

Patent document 3: Japanese Unexamined Patent Publication H05-200858 bulletin

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

Patent document 5: Japanese Unexamined Patent Publication 2000-173855 bulletin.

Summary of the invention

Problems to be solved by the invention

First the present invention is completed in view of the aforementioned technical background completes, and its purpose is to provide windability and resistance to scraping is excellent Styrene-based resin stretched film.

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

It should be noted that stretched film of the invention is properly termed as making the alignment films of molecular chain orientation by stretching, exist below Alignment films are otherwise referred to as in first present invention.

The solution to the problem

The present inventor to achieve the goals above has made intensive studies various inert particles.In research, to energy Enough the porous particle of the generations of voids such as polyester is inhibited also to be studied, but styrene-based resin is unable to get The same effect with polyester film etc..However, it is surprising that the inventors discovered that by porous particle and silicone oil and after using, It is able to solve the above problem, so as to complete first present invention.

As a result, according to first present invention, a kind of stretched film (being known as alignment films in first present invention below), the drawing are provided Stretching film includes resin combination, which contains the styrenic of syndiotactic structure, average grain diameter is 0.5 ~ 5.0 μm porous particle and silicone oil, wherein on the basis of the quality of the resin combination, the content of porous particle is 0.01 matter % or more and 3 mass % ranges below are measured, on the basis of the quality of the porous particle, the content of silicone oil is the model of 0.1 ~ 3 mass % It encloses.

In addition, the present inventor has made intensive studies to achieve the goals above, as a result, it has been found that, there will be particular surface special Property porous silica silicon particle cooperate in the polystyrene resin of syndiotactic structure made of resin combination can be easy The gap that ground obtains the dispersed excellent of the particle and generates when forming stretched film with matrix resin dilution as needed It is small, as thin film capacitor used time operability, dielectric breakdown characteristic, resistance to scraping etc. also good stretched film, so as to complete Two present invention.

As a result, according to second present invention, a kind of stretched film is provided, which includes resin combination, the resin combination The polystyrene resin and average grain diameter A that object contains syndiotactic structure are 0.5 ~ 5 μm, DBA value is 200 mMs/kg or less Porous silica silicon particle, wherein on the basis of resin combination amount of substance, the content of the porous silica silicon particle is 0.01 Quality % or more and 3 mass % or less.

As described above, according to the present invention, providing above-mentioned first present invention and second present invention.Specifically, providing one kind Stretched film, which is characterized in that the stretched film includes resin combination, and the polystyrene which contains syndiotactic structure is poly- Object and average grain diameter are closed as 0.5 ~ 5.0 μm of porous particle, on the basis of the quality of the resin combination, the content of porous particle For 0.01 mass % or more and 3 mass % ranges below, the stretched film meet any one of following (1), (2):

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

(2) porous particle be average grain diameter A be 0.5 ~ 5 μm, DBA value is 200 mMs/kg porous silica below Particle.

The effect of invention

First stretched film of the invention is in the polystyrene with syndiotactic structure using electrical characteristic and excellent heat resistance While based polymer, additionally it is possible to resulting alignment films be made to have the windability and resistance to scraping of height.

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

Second stretched film of the invention, in the polystyrene resin of the syndiotactic structure of heat resistance and excellent electrical characteristic The porous silica silicon particle with specified particle diameter and particular surface property containing specific quantity, therefore the dispersed pole of the particle It is good, and the gap generated by the particle is small, and operability, dielectric breakdown characteristic, resistance to scraping are excellent, particularly suitable as film Capacitor is used.

Specific embodiment

Firstly, being illustrated to the first alignment films of the invention.

Alignment films of the invention include resin combination, which contains the polystyrene polymerization of syndiotactic structure Object, the porous particle and silicone oil that average grain diameter is 0.5 ~ 5.0 μm.

Polystyrene resin (hereinafter sometimes referred to " the syndiotactic polytyrene tree with syndiotactic structure in the present invention Rouge " or " SPS ") be the resin with following stereochemical structure: the benzene relative to the main chain by carbon-carbon bond formation, as side chain Base, substituted-phenyl are alternately located in opposite direction.Usual steric regularity (tacticity) is total by the nuclear-magnetism using isotope carbon Vibration method (¹³C-NMR method) it is quantified.Specifically, can with continuous multiple structural units there are ratios to indicate, such as There are, with the expression of two unit groups (diad), there are, with the expression of three unit groups (triad), there are single with five at 5 at 3 at 2 Tuple (pentad) indicates.The polystyrene resin of syndiotactic structure in the present invention refers to, have two unit groups be 75% with It is upper, preferably 85% or more or five unit group be 30% or more, preferably 50% or more degree of syndiotacticity polystyrene, poly- (ring-alkylated styrenes), poly- (halogenated styrenes), poly- (alkoxystyrene), poly- (vinyl benzoate) or their phenyl ring A part be hydrogenated made of polymer or their mixture or the copolymer containing these structural units.It should say It is bright, it is used as poly- (ring-alkylated styrenes) herein, 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 enumerate polystyrene, poly- (p-methylstyrene), it is poly- ( Methyl styrene), poly- (p-tert-butylstyrene), poly- (p-chlorostyrene), poly- (m-chlorostyrene), poly- (pfluorostyrene), And the copolymer of styrene and p-methylstyrene, wherein preferably polystyrene.

In turn, contain in polystyrene resin of the invention in the case that copolymer composition uses as copolymer, as Its comonomer, other than the monomer of polystyrene resin as described above, can also use 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 acid anhydrides, acrylonitrile isopolarity vinyl monomer etc..

In addition, the weight average molecular weight of the polystyrene resin of the syndiotactic structure is preferably 1.0 × 10⁴~3.0×10⁶, into One step is preferably 5.0 × 10⁴~1.5×10⁶, particularly preferably 1.1 × 10⁵~8.0×10⁵.By making weight average molecular weight 1.0 ×10⁴It above, is preferably 5.0 × 10⁴Above, 1.1 × 10 are particularly preferably⁵More than, available strength elongation characteristic is excellent The formed products such as the film that different, heat resistance further increases.In addition, if weight average molecular weight is 3.0 × 10⁶It below, is preferably 1.5 ×10⁶Below, 8.0 × 10 are particularly preferably⁵Hereinafter, then make tensile stress in optimum range, it is not susceptible to be broken when film etc. Deng.

Porous particle contained in alignment films of the invention, needing its average grain diameter is 0.5 ~ 5 μm, preferably 0.8 ~ 2.5 μ m.In the case where its average grain diameter is less than 0.5 μm, the smoothness (sliding り) of film is insufficient, windability and operational insufficient. On the other hand, in the case where being greater than 5 μm, the diameter in the gap formed around particle by stretching etc. becomes larger, and it is not preferable. In addition, needing the content of the particle is 0.01 ~ 3 mass %, further preferably 0.02 ~ 1 on the basis of resin combination amount of substance The range of quality %, particularly preferably 0.05 ~ 0.5 mass %.Its content smoothness if insufficient lower limit is insufficient and windability shortage. On the other hand, in the case where being more than the upper limit, other than resistance to scraping is insufficient, dielectric breakdown characteristic is also impaired, film is drawn Stretching property.

From the above point of view, the average grain diameter of porous particle used in the present invention be preferably 0.5 ~ 5 μm, it is further excellent It is selected as 0.8 ~ 2.5 μm.In turn, the compression ratio of porous particle used in the present invention is (when 0.2gf load: using Shimadzu Seisakusho Ltd. Slight compression processed test MCTM-200 is measured) be preferably 20 ~ 90%, particularly preferably 50 ~ 85% range.The value not foot In the case where limit, for example, when stretched film is made resistance to scraping improvement effect it is insufficient.On the other hand, in the case where being more than the upper limit, example When stretched film is such as made, which crushes and makes to convex to form insufficient, windability improvement effect and become smaller.By making compression ratio In above-mentioned proper range, the particle is appropriate due to stress whens being processed into stretched film etc. to be deformed, and is made it easy to more highly Take into account windability and resistance to scraping.

As such porous particle, particle commonly known per se can be used, particularly preferably enumerate porous silica Particle.The manufacturing method of porous silica silicon particle is not particularly limited, and can be used existing by sol-gal process, precipitation method etc. There is known particle made of well known method.Wherein, preferably pore volume is 0.4 ~ 2.5ml/g, particularly preferably 1.2 ~ 1.8ml/g Range particle, additionally, it is preferred that average pore size be 5 ~ 25nm range particle.

As described above, alignment films of the invention also and use silicone oil.On the basis of the quality of the porous particle, which contains Amount is the range of 0.1 ~ 3 mass %, preferably 0.2 ~ 2.0 mass %.In the case where the content deficiency lower limit of silicone oil, the porous particle Dispersibility be deteriorated and formed coarse agglutinating particle make be film-made draftability it is bad, furthermore resistance to scraping is not sufficiently effective.On the other hand, exist In the case where more than the upper limit, silicone oil can be oozed out on the surface of film sometimes and pollutes manufacturing procedure.

Silicone oil referred to herein refers to, using dialkylsiloxane ingredient as the organo-silicon compound of predominant repeat unit, can arrange Enumerate the silicone oil that siloxanes key is 2000 linear chain structures below.Such as can enumerate: the side chain of polysiloxanes, end are first A part of the dimethyl polysiloxane of base and then polysiloxanes side chain is methyl phenyl silicone, the polysiloxanes of phenyl A part of side chain is that the pure silicons such as the methylhydrogenpolysi,oxane of hydrogen are oily (straight silicone oil, common silicone oil)；Other The modified silicon oil of organic group is introduced in side chain, end.As organic group introduced in modified silicon oil, can enumerate: Monoamine base, two amidos, amino, epoxy group, alicyclic epoxy group, 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.

The fitting method of silicone oil in the film is not particularly limited, above-mentioned porous from being easy to be present in silicone oil selectively From the viewpoint of particle surface, it is preferred that be directly added dropwise or be coated in above-mentioned porous particle, by spraying spraying etc. after, put Enter the method stirred in mixing machine etc..

Through silicone oil attachment, treated that porous particle can add in the polymerization stage of resin material, can also be using melting Mixing method is added to by polymerizeing in resulting resin material, without being particularly limited to.For example, it may be by the porous particle powder The method for supplying from the same supply mouth of melting mixing machine with resin material and carrying out melting mixing；Or first to band gas vent (vent) resin material is put into the melting mixing machines such as twin-screw mixer extruder, then the porous particle is added to powder Position that the resin material has melted and the method for carrying out melting mixing.Wherein, the particle 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 gas vent Method.According to this method, thus it is speculated that since the particle is attached to the surface of resin granular material or toner, inside kneading machine When being crushed, the contact interval of the particle and resin is minimum, so dispersibility further increases.

As the twin-screw mixer extruder with gas vent, it is preferable to use following device: the adding mouth setting of particle is being matched It is placed in portion full thread (full flight) of the screw rod inside the twin-screw mixer extruder with gas vent, from above-mentioned addition It is provided at least the one of opening's edge screw rod axis direction downstream side with for making particle be kneaded the feeding blade (sending the り wing) of dispersion With the rotor segment (rotor segment) for returning to blade (the Reversal wing).Herein, gas exhaust piping (vent line) is for removing By-product from resin.In addition, the twin-screw mixer extruder with gas vent preferably has rotor segment at 1 ~ 3.If irrotationality Turn scraper plate then the particle mixing dispersion reduce, if being more than at 3 if rotor segment resin propulsive force reduction and easily occur curved It rolls over (bent up).Additionally, it is preferred that having the kneading disk of the mixing dispersion for supplementing the porous particle.

For alignment films of the invention, the quantity for the coarse agglutinating particle that maximum length is 25 μm or more in film is excellent It is selected as 10/m²Hereinafter, further preferably 5/m²Hereinafter, particularly preferably 3/m²Below.The number of coarse agglutinating particle Film surface generates non-uniform protrusion if more than the upper limit, and winding offset becomes when stretch wrap film (rollback Off ィ Le system) is made Difference, processability reduce, therefore are not suitable for.In addition, becoming the starting point of fracture in film stretching process, draftability is unstable, therefore not It is preferred that.

In the range of not interfering the object of the invention, alignment films of the invention can be with other than adding the porous particle Add the particle B different from the porous particle.It is preferably of the invention since above-mentioned porous particle will form biggish protrusion Particle B plays to form smaller raised role.From this viewpoint, the preferably partial size of particle B is smaller than above-mentioned porous particle, by Small in partial size therefore preferably not agglutinophilic particle.The average grain diameter A of particle B is preferably 0.01 μm more than and less than 0.5 μm.Into One step is preferably 0.1 μm more than and less than 0.4 μm.If average grain diameter A deficiency lower limit, is unable to get sufficient smoothness, It is not preferable.On the other hand, if average grain diameter A is more than 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 particle B of the invention is preferably 0.5 weight % or less.If content mistake More, then the frequency in the gap as caused by particle increases sometimes or dielectric breakdown voltage reduces.From this viewpoint, further Preferably 0.5 weight % or less, particularly preferably 0.2 weight % or less.

As the type of particle B, various particles, the preferably small spherical particle of specific surface area can be used.It should be noted that It is of the invention it is spherical refer to, when carrying out image analysis to the shape of particle, the ratio between maximum major diameter and area equivalent circle diameter are 1.5 It below, is preferably 1.2 shapes below.It as specific particle, is not particularly limited, can enumerate (1) two well known to itself Silica (including hydrate, silica sand, quartz etc.)；(2) aluminium oxide of various crystal habits；(3) contain the 30 above SiO of weight %₂ Silicate (such as clay mineral, the alumino-silicate (including calcined material, hydrate), chrysotile, zirconium of amorphous state or crystalline state of ingredient 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 powder, bead etc.)；(13) carbonate of Ca and Mg；(14) fluorite；(15) point is brilliant Stone-type oxide；(16) it is crosslinked organic granular (organosilicon, granules of polystyrene etc.).From obtaining good smoothness, resistance to scraping This viewpoint consider, preferably enumerate spherical silica particles, spherical alumina particle, crosslinking organic granular and it Composite particles, particularly preferably spherical organic silicon particle.Using the case where spherical organic silicon resin particle is as particle B Under, when and when using polyphenylene oxide as aftermentioned thermoplasticity noncrystalline resin, make heat resistance especially high due to synergistic effect.

Alignment films of the invention include resin combination, and the polystyrene which contains above-mentioned syndiotactic structure is poly- It closes object, the porous particle and silicone oil that average grain diameter is 0.5 ~ 5.0 μm, is by the way that resin combination edge is at least uniaxial Direction, preferably biaxially oriented stretch, to make alignment films made of molecular chain orientation.

Moreover, resin combination of the invention preferably comprises following thermoplasticity noncrystalline resin Y.Thermoplasticity amorphous referred to herein Resin Y is preferably the heat for being Tg more higher than SPS using the glass transition temperature Tg that DSC (differential scanning calorimetry (DSC)) is found out Plasticity noncrystalline resin.If cooperating this analog thermoplastic noncrystalline resin Y in SPS, the glass transition of mixture is served not only as Temperature Tg is improved, and heat resistance improves, and the dielectric breakdown voltage under high temperature also improves.In addition, can also make the hot ruler of alignment films Very little to have good stability, draftability also improves.From this viewpoint, the glass transition temperature Tg of thermoplasticity noncrystalline resin Y is preferred It is 150 DEG C or more, further preferably 180 DEG C or more, particularly preferably 200 DEG C or more.Thermoplasticity noncrystalline resin Y joined together Glass transition temperature Tg it is higher, the improvement effect of the said effect such as thermal dimensional stability is bigger.If in view of melting is squeezed Out etc., then the substantive upper limit 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 raising and and antioxygen There is synergistic effect, or heat resistance, dimensional stability improves but also dielectric breakdown voltage because not only making when agent combines It further increases, therefore particularly preferably.As polyphenylene oxide resin used herein, conventionally known resin can be enumerated, such as: it is poly- (2,3- dimethyl -6- ethyl -1,4- phenylate (phenylene ether)), poly- (2- methyl -6- chloromethyl -1,4- phenylate) gather (2- methyl -6- ethoxy -1,4- phenylate), poly- (2- methyl -6- normal-butyl -1,4- phenylate), it is poly- (isopropyl -1 2- ethyl -6-, 4- phenylate), poly- (2- ethyl -6- n-propyl -1,4- phenylate), poly- (2,3,6- trimethyl -1,4- phenylate), poly- (2- (4 '-methyl Phenyl) -1,4- phenylate), poly- (the bromo- 6- phenyl -1,4- phenylate of 2-), poly- (2- methyl -6- phenyl -1,4- phenylate), poly- (2- benzene Base -1,4- phenylate), poly- (the chloro- 1,4- phenylate of 2-), poly- (2- methyl-1,4- phenylate), poly- (the chloro- 6- ethyl -1,4- phenylate of 2-), Poly- (the bromo- 1,4- phenylate of the chloro- 6- of 2-), poly- (2,6- diη-propyl -1,4- phenylate), poly- (2- methyl -6- isopropyl -1,4- benzene Ether), poly- (the chloro- 6- methyl-1 of 2-, 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. Polymers and their copolymer.In addition, being also suitable for using these resins after the modifier modifications such as maleic anhydride, fumaric acid Modifier.In turn, it can also use the vinyl aromatic compounds such as styrene and above-mentioned polyphenylene oxide graft copolymerization or embedding Copolymer made of Duan Gongju.Wherein, particularly preferably poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylate).

For the intrinsic viscosity of polyphenylene oxide resin, in chloroform, when being measured at 30 DEG C, the preferably model of 0.2 ~ 0.8dl/g It encloses, the range of more preferably 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.On the other hand, when being greater than 0.8dl/g, there is the mobility reduction of gained resin combination, melt-shaping is film etc. When processing become difficult trend.Polyphenylene oxide resin can be used in combination two or more, polyphenylene oxide tree that at this time can be different by intrinsic viscosity Rouge mixes and reaches required intrinsic viscosity.

Alignment films of the invention cooperate 5 mass % or more and 48 mass % are below preferably with respect to the quality of the alignment films Above-mentioned thermoplasticity noncrystalline resin Y.By the amount cooperation thermoplasticity noncrystalline resin Y with above range, excellent heat resistance can be made, and Increase the improvement effect of dielectric breakdown voltage.I.e., it is possible to the dielectric breakdown voltage under improving high temperature.In the case that content is very few, Heat resistance has the tendency that variation, and the improvement effect of dielectric breakdown voltage has the tendency that reduction, the improvement effect of draftability Not enough.From this viewpoint, the content of thermoplasticity noncrystalline resin Y is more preferably 8 mass % or more, further preferably 11 mass % Above, 20 mass % or more are particularly preferably.In addition, the crystallinity of SPS has the tendency that reduction, film in the case that content is excessive Heat resistance have the tendency that variation.From this viewpoint, the content of thermoplasticity noncrystalline resin Y be more preferably 45 mass % or less, into One step is preferably 40 mass % or less, particularly preferably 35 mass % or less.

Certainly, in the range of not interfering the purpose of the present invention, alignment films of the invention are in addition to containing above-mentioned SPS, thermoplastic Property noncrystalline resin Y other than, can also be further and with other resins.

<antioxidant>

Alignment films of the invention preferably comprise antioxidant.As antioxidant, can be capture the free radical generated and It prevents the main anti-oxidant of oxidation or the peroxide of generation is decomposed and prevents any in the auxiliary antioxidant of oxidation Kind.Phenolic antioxidant, amine antioxidant can be enumerated as main anti-oxidant, phosphorus system can be enumerated as auxiliary antioxidant Antioxidant, sulfur antioxidant.Wherein preferred main anti-oxidant, particularly preferred phenolic antioxidant.

In addition, antioxidant preferably its pyrolysis temperature is 250 DEG C or more.If pyrolysis temperature is high, the medium under high temperature The improvement effect of breakdown voltage increases.In the case that pyrolysis temperature is too low, antioxidant itself is pyrolyzed when melting extrusion, is deposited Trend the problems such as being easy to produce pollution process, polymer coloration is yellow, not preferably.From this viewpoint, antioxidant Pyrolysis temperature be more preferably 280 DEG C or more, further preferably 300 DEG C or more, be particularly preferably 320 DEG C or more.The present invention Antioxidant be preferably to be not easy the antioxidant that is pyrolyzed, although the preferably high antioxidant of pyrolysis temperature, actually its The upper limit is 500 DEG C or less Zuo You.

Additionally, it is preferred that the fusing point of antioxidant is 90 DEG C or more.It is anti-oxidant in melting extrusion in the case that fusing point is too low Agent is faster melted than polymer, there are polymer the screw feed partial slip of extruder trend.Make polymer as a result, Supply it is unstable, generate film uneven thickness (thick body spot) be deteriorated the problems such as.From this viewpoint, the fusing point of antioxidant is more Preferably 120 DEG C or more, further preferably 150 DEG C or more, particularly preferably 200 DEG C or more.On the other hand, antioxidant In the case that fusing point is excessively high, antioxidant is difficult to melt when melting extrusion, and there are the trend that the dispersion in polymer is deteriorated.By This, generates the additive effect of antioxidant only in local the problems such as occurring.From this viewpoint, the fusing point of antioxidant is preferably 300 DEG C hereinafter, more preferably 250 DEG C hereinafter, further preferably 220 DEG C hereinafter, particularly preferably 170 DEG C or less.

As antioxidant as described above, commercially available product can also be directly used.It is enumerated as commercially available product, such as preferably Out: pentaerythrite four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester] (Ciba Specialty Chemicals company System: trade name IRGANOX1010), N, bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propiono] hydrazine (Ciba of N '- Specialty Chemicals corporation: trade name IRGANOX1024), N, bis- [3- (bis- uncles of 3,5- of N '-hexane -1,6- diyl Butyl -4- hydroxy phenyl) propionamide] (Ciba Specialty Chemicals corporation: trade name IRGANOX1098) etc..

On the basis of the quality of alignment films, the content of antioxidant is preferably 0.1 mass % or more and 5 mass % or less.It is logical It crosses and antioxidant is contained with the content of above-mentioned numberical range, the improvement effect of dielectric breakdown voltage can be increased.Antioxidant In the case that content is very few, what insufficient, dielectric breakdown voltage improvement effect that there are the additive effects of antioxidant reduced becomes Gesture.From this viewpoint, the content of antioxidant be more preferably 0.2 mass % or more, further preferably 0.5 mass % or more, Particularly preferably 0.7 mass % or more.On the other hand, in the case that content is excessive, antioxidant has easy agglutination in biaxially-stretched film Trend, the defect as caused by antioxidant had increased trend, the improvement effect of dielectric breakdown voltage made due to the defect Decline.From this viewpoint, the content of antioxidant is more preferably 3 mass % or less, further preferably 2 mass % or less, spy It You Xuanwei not 1.5 mass % or less.

These antioxidants can be used alone, and can also be used in combination two or more.

<other additives>

In the range of not interfering the purpose of the present invention, such as in order to further improve formability, mechanics physical property, superficiality Other resin components different from thermoplasticity noncrystalline resin Y can be contained Deng, alignment films of the invention, or addition is antistatic The additives such as agent, colorant, weather resisting agent.As long as in addition, can also be used in combination on a small quantity in the range of not interfering the purpose of the present invention Inert particle other than porous particle and above-mentioned particle B.

<metal layer>

Alignment films of the invention are by being made capacitor in for example, at least single side superimposed layer metal layer.For metal layer Material is not particularly limited, such as can enumerate aluminium, zinc, nickel, chromium, tin, copper and their alloy.In turn, these metals Layer can be aoxidized in right amount.In addition, in order to be simply forming metal layer, metal layer is preferably the vapor deposition for using vapour deposition method to be formed Type metal layer.

In addition, when carrying out lamination to metal layer, by the way that metal is further arranged on the surface of coating layer of the invention Layer, can make substrate layer and metal layer have the bonding force of appropriateness, implement gold when the processing such as winding in the manufacture of thin film capacitor Belonging to layer will not remove, and play the function as capacitor.In turn, while making coating layer and metal layer that there is appropriate adhesiveness, i.e., Remove the coating layer to discharge and surface can be small first from film, only metal layer and coating layer is destroyed, and film is not It is destroyed, thus without short-circuit condition is caused, the improvement effect of dielectric breakdown voltage can be increased.

<film characteristics>

(refractive index of thickness direction)

The refractive index in alignment films preferred thickness direction of the invention is 1.575 or more and 1.635 or less.By making thickness side To refractive index reach above-mentioned numberical range, dielectric breakdown voltage can be further increased.In addition, film in thin film fabrication process The frequency of fracture reduces, and is easy to improve production efficiency.From this viewpoint, the refractive index of thickness direction be preferably 1.620 hereinafter, Further preferably 1.615 hereinafter, particularly preferably 1.610 or less.On the other hand, the too low situation of the refractive index of thickness direction Under, dielectric breakdown voltage has the tendency that reduction.

In addition, the frequency of high-insulativity film film breaks in the manufacturing process of capacitor of the invention increases, capacitor The production efficiency of device is easily reduced.In turn, there are the trend that the uneven thickness of film is deteriorated, it is difficult to obtain the capacitor of stay in grade Device.From this viewpoint, the refractive index of thickness direction is preferably 1.590 or more, is more preferably 1.595 or more, especially excellent It is selected as 1.600 or more.

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

(film thickness)

The thickness of alignment films of the invention is not particularly limited, and examines in terms of more thin more be easy to appear effect of the invention Consider, particularly preferably 0.4 μm more than and less than 6.5 μm.Further preferably 0.4 μm more than and less than 6.0 μm, particularly preferably 0.5 μm more than and less than 3.5 μm.In addition, by reaching above-mentioned film thickness, the high capacitor of available electrostatic capacitance.

(voidage)

Alignment films of the invention are free of gap preferably on the surrounding parenchyma of porous particle.Sky is substantially free of in the present invention Gap refers to, is free of gap, or the gap containing the degree that particle will not be caused to fall off or containing will not make dielectric breakdown voltage The gap of reduced degree.Refer to when measuring aftermentioned voidage, voidage is 50% or less, particularly preferably 30% or less. It should be noted that not only work in-process can cause filler to fall off, pollute process, and surface is thick if voidage is more than the upper limit Rugosity changes, and the winding for generating film roll is bad.

(dielectric breakdown voltage (BDV))

It is preferred that the dielectric breakdown voltage (BDV) of alignment films of the invention at 120 DEG C is 450kV/mm or more.Dielectric breakdown Voltage indicates there is excellent dielectric breakdown voltage at high temperature in above-mentioned numberical range.The dielectric breakdown voltage is more Preferably 500kV/mm or more, further preferably 520kV/mm or more.

In addition, the deviation of alignment films of the invention for dielectric breakdown voltage, standard deviation be preferably 40kV/mm with Under, more preferably 30kV/mm or less, further preferably 20kV/mm or less.

Alignment films of the invention by using specific porous particle, the average value of dielectric breakdown voltage can be increased and And reduce its standard deviation, the reliability of material when can be improved the electrically insulating material as capacitor etc..That is, due to that can subtract The standard deviation of small dielectric breakdown voltage, therefore can inhibit the reduction of dielectric breakdown voltage minimum value, increase dielectric breakdown voltage Average value.

<manufacturing method of film>

Alignment films of the invention can substantially be obtained using the method that existing known or this field is accumulated.With Under, the manufacturing method for obtaining alignment films of the invention is described in detail.It should be noted that alignment films of the invention can be single shaft Alignment films can also be biaxially oriented film, from the aspect of production efficiency, the balance of physical property, preferably Biaxially oriented film.Hereinafter, with It is illustrated for Biaxially oriented film.

Firstly, as described above, the resin combination progress heating melting that will be combined with SPS, porous particle and silicone oil, is made Non-stretched.Specifically, more than the fusing point (Tm, unit: DEG C) of resin combination and at (Tm+50 DEG C) temperature below into Row heating melting, squeezes out slabbing, and cooling and solidifying obtains non-stretched.The intrinsic viscosity that gained is non-stretched is preferably 0.35 ~ The range of 0.9dl/g.

Then, biaxial stretch-formed to this non-stretched progress.Stretching can be to longitudinal (mechanical axis direction) and laterally (with machinery Axis direction and the vertical direction of thickness direction) it stretches simultaneously, it can also successively stretch in any order.Such as the feelings successively stretched Under condition, first along uniaxial direction, more than (- 10 DEG C of the glass transition temperature of resin combination (Tg, unit: DEG C)) and (Tg+ 70 DEG C) at temperature below, with 3.2 times or more and 5.8 times or less, preferably 3.3 times or more and 5.4 times or less, it is further excellent It is selected as 3.4 times or more and 5.0 times of multiplying powers below is stretched, then along the direction orthogonal with the single shaft direction, in Tg or more And at (Tg+80 DEG C) temperature below, with 3.8 times or more and 5.9 times or less, preferably 4.0 times or more and 5.5 times or less, more Preferably 4.1 times or more and 5.1 times or less, further preferably 4.2 times or more and 4.9 times of multiplying powers below are stretched.Into And the situations that area stretch multiplying power (=vertical stretching ratio × horizontal stretching ratio) is 12.0 times or more, it can obtain having above-mentioned flat The film of surface orientation coefficient, therefore it is preferred that.If area stretch multiplying power reduces, heat resistance is deteriorated, not preferably.Therefore, area is drawn It stretches multiplying power and is more preferably 13.0 times or more, further preferably 13.5 times or more, particularly preferably 14.0 times or more.In addition, such as Fruit area stretch multiplying power is excessively high, then is easily broken when being film-made, stretching, not preferably.From this viewpoint, area stretch multiplying power is excellent It is selected as 22 times or less, more preferably 20 times or less, further preferably 18 times or less, particularly preferably 17 times or less.

It should be noted that in the present invention, can by non-stretched on piece or by this non-stretched preferably along longitudinal direction into Coating is used to form the masking liquid of coating layer on monadic stretching membrane made of row is uniaxially stretched, to form coating layer.

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

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

<stretched film>

Second stretched film of the invention includes resin combination, which contains the polystyrene of syndiotactic structure The porous silica silicon particle that resin (hereinafter sometimes referred to SPS) and average grain diameter A are 0.5 ~ 5.0 μm.

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

Below unless stated otherwise, for porous silica silicon particle contained by stretched film of the invention, can carry out with it is upper The porous silica silicon particle illustrated in first present invention is stated similarly to illustrate.It should be noted that it is different from first present invention, the Have specific specific surface area and DBA value in two present invention, therefore can not and use silicone oil.

Porous silica silicon particle further requirement DBA value (di-n-butyl amine adsorbance) used in second present invention is 200 mMs/kg or less, preferably 100 mMs/kg or less.It is not only more in the case that DBA value is greater than 200 mMs/kg Dispersion of the hole silica dioxide granule in resin combination is deteriorated, and is also easy to produce when being configured to stretched film between resin and particle Gap, it is not preferable.It should be noted that DBA value described herein is the toluene solution processing porous silica with di-n-butyl amine Di-n-butyl amine adsorbance (adsorbance (mM) of the di-n-butyl amine relative to 1kg particle) when silicon particle.

The manufacturing method of the porous silica silicon particle is not particularly limited, and can be readily derived in the following manner: For the surface of the porous silica silicon particle using the conventionally known method manufacture such as sol-gal process, the precipitation method, example is utilized Such as alkylalkoxysilane compounds, silicon nitrogen silane compound are handled, and are modified to the silanol group of particle surface, Thus it obtains.In the case that particle surface silanol group is more, reduced with the compatibility of the polystyrene resin of syndiotactic structure, And dispersibility of the particle in resin combination reduces.In addition, easily being produced between resin and particle when being not only configured to stretched film Raw gap, and the activity of particle surface rises is easy to produce the drawbacks such as be aggregated again of particle when being matched in resin material.

In addition, porous silica silicon particle be preferably primary particle agglutination made of agglutinating particle, further preferably this one Secondary grain diameter is 0.01 ~ 0.1 μm, pore volume is within the scope of 0.5 ~ 2.0ml/g, in addition, average pore size is preferably in 5 ~ 25nm model In enclosing.Think that, by meeting the important document, due to the stress being processed into whens stretched film etc., which moderately deforms, make around particle The diameter for being formed by gap reduces.

Described above second stretched film of the invention preferably comprises other than containing above-mentioned porous silica silicon particle Average grain diameter A is 0.01 μm of particle (hereinafter sometimes referred to inert particle C) more than and less than 0.5 μm.By containing the inertia Particle C is able to maintain high dielectric breakdown voltage and keeps the smoothness of stretched film good, and can obtain windability excellent drawing Stretch film.In the case that the average grain diameter A of inert particle C is too small, the improvement of smoothness has the tendency that reduction, windability improvement Effect also reduces.On the other hand, in the case where excessive, the excessive height of the low protrusion of film surface causes smoothness excessively high, from And the windability reductions such as end face offset are also easy to produce in winding.In addition, the gap in film has the tendency that increase, resistance to scraping, Jie Matter breakdown voltage reduces.From this viewpoint, the average grain diameter A of inert particle C be preferably 0.05 μm more than and less than 0.5 μm, Further preferably 0.1 μm more than and less than 0.5 μm, particularly preferably 0.2 ~ 0.4 μm.It should be noted that it is preferred that inert particle C Average grain diameter A be less than above-mentioned porous silica silicon particle average grain diameter A, the difference between the two is preferably 0.2 μm or more.

The spherical particle that inert particle C preferable particle size ratio (major diameter/minor axis) is 1.0 ~ 1.3.Partial size is than further preferred It is 1.0 ~ 1.2, particularly preferably 1.0 ~ 1.1.If partial size ratio can be such that windability raising imitates in above-mentioned numberical range The improvement effect of fruit and dielectric breakdown voltage is bigger.

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

Spherical organic silicon resin particle is most preferably as inert particle C.Use spherical organic silicon resin particle as In the case where inert particle, and when using polyphenylene oxide as aftermentioned thermoplasticity noncrystalline resin, heat resistance is made by synergistic effect It is especially high.

Content of the inert particle C in 100 mass % of resin combination is preferably 0.01 ~ 3 mass %, more preferably 0.05 ~ 2 mass %, further preferably 0.1 ~ 0.5 mass %, particularly preferably 0.1 ~ 0.3 mass % or less.By within the above range Containing the inert particle, it is able to maintain high dielectric breakdown voltage and keeps the operability of film good.

It should be noted that inert particle can be added directly or as master batch chips (マ ス タ ー チ ッ プ), so that will When resin combination melt-shaping without inert particle is film, the inert particle content in gained film is in above range It is interior.

Second stretched film of the invention preferably also contains thermoplasticity noncrystalline resin.For thermoplasticity amorphous tree described herein Rouge can carry out similarly illustrating with the thermoplasticity noncrystalline resin illustrated in above-mentioned first present invention.

In addition, in the range of not interfering the purpose of the present invention, in addition to containing above-mentioned in the second stretched film of the invention Other than SPS, thermoplasticity noncrystalline resin, can also and with other resins.

Second stretched film of the invention preferably also contains antioxidant.As antioxidant, can carry out and above-mentioned first The antioxidant illustrated in invention similarly illustrates.

In the range of not interfering the purpose of the present invention, in order to further improve such as film formation property, mechanics physical property, superficiality Other resin components different from thermoplasticity noncrystalline resin can also be contained Deng, the second stretched film of the invention, or addition is anti- The additives such as electrostatic agent, colorant, weather resisting agent.In addition, can also be used in combination on a small quantity in the range of not interfering the purpose of the present invention Inert particle other than above-mentioned particle.

For the stretched film of the invention for second, maximum length present in the refractive index and film for thickness direction For 25 μm or more of coarse agglutinating particle, can carry out similarly illustrating with the content illustrated in above-mentioned first present invention.

Second stretched film of the invention is free of gap preferably on the surrounding parenchyma of porous silica silicon particle.Essence herein It is upper identical without the meaning illustrated in gap and first present invention.It should be noted that not only adding if voidage is greater than 50% Particle can be caused to fall off in work, pollute process, and surface roughness changes and generate the operability such as winding is bad of film roll It reduces, in addition, dielectric breakdown voltage reduces and its deviation is (dielectric breakdown characteristic is easily reduced) also easy to increase.

The thickness of second stretched film of the invention is not particularly limited, in terms of more thin more be easy to appear effect of the invention Consider, particularly preferably 0.4 ~ 6.5 μm.Further preferably 0.4 ~ 6.0 μm, particularly preferably 0.5 ~ 3.5 μm.On reaching State film thickness, the high capacitor of available electrostatic capacitance.

Dielectric breakdown voltage (BDV) of further preferred second stretched film of the invention at 120 DEG C be 450V/ μm with On.Dielectric breakdown voltage, which meets the important document, indicates there is excellent dielectric breakdown voltage at high temperature.The dielectric breakdown Voltage is more preferably 500V/ μm or more, further preferably 520V/ μm or more.

In addition, the standard deviation of above-mentioned dielectric breakdown voltage is preferably 40V/ μm or less, more preferably 30V/ μm or less, into One step is preferably 20V/ μm or less.The standard deviation, which meets above-mentioned important document, indicates that the reduction of the dielectric breakdown voltage of part is small (partially Difference is small), the reliability of material when electrically insulating material as capacitor etc. can be improved.

The stretched film of the invention for second, preferably its at least single side centerline average surface roughness Ra be 7 ~ 89nm.By making centerline average surface roughness Ra within this range, windability improvement effect can be increased.In addition, can So that resistance to blocking (blocking resistance) improves, the appearance of volume is good.Centerline average surface roughness Ra is too low In the case where, smoothness has the tendency that too low, windability improvement effect reduces.On the other hand, in the case where excessively high, smoothness Have the tendency that excessively high, when winding easily causes end face offset etc., windability improvement effect reduces.From this viewpoint, center The lower limit of line average surface roughness Ra is more preferably 11nm or more, further preferably 21nm or more, particularly preferably 31nm More than.In addition, the upper limit of centerline average surface roughness Ra be more preferably 79nm hereinafter, further preferably 69nm hereinafter, Particularly preferably 59nm or less.

In addition, the stretched film of the invention for second, 10 mean roughness Rz of preferably its at least single side are 200 ~ 3000nm.By making 10 mean roughness Rz within this range, windability improvement effect can be increased.10 average roughness Spend Rz it is too low in the case where, the windability raisings such as de-gas has the tendency that reduction when rolling coiled, and film is easy to slide laterally Effect reduces.In particular, the toughness (Off ィ Le system waist) of film disappears, therefore de-gas in the case where film thickness is relatively thin Have the tendency that further decreasing, windability improvement effect further decreases.On the other hand, 10 mean roughness Rz are excessively high In the case of, coarse protrusion has increased trend, and the improvement effect of dielectric breakdown voltage reduces.From this viewpoint, 10 points average The lower limit of roughness Rz is more preferably 600nm or more, further preferably 1000nm or more, particularly preferably 1250nm or more. In addition, the upper limit of 10 mean roughness Rz is more preferably 2600nm or less, is more preferably 2250nm or less, particularly preferred For 1950nm or less.

<manufacturing method of film>

Described above second stretched film of the invention can be used and above-mentioned first other than it can not add silicone oil The same manufacturing method of the manufacturing method illustrated in invention is manufactured.

<resin combination>

In the manufacture of second stretched film of the invention it is preferable to use resin combination, be the polyphenyl in above-mentioned syndiotactic structure Resin combination made of melting mixing porous silica silicon particle in vinylite.

The average grain diameter B of porous silica silicon particle used herein is preferably 0.5 ~ 5 μm, particularly preferably 0.8 ~ 3.0 μ The range of m.Porous silica in the case that the average grain diameter is less than 0.5 μm, whens there are melt-shaping being film etc. in film The average grain diameter A of silicon particle reduces, and smoothness is insufficient, windability, operational also insufficient trend.On the other hand, it is greater than 5 μm In the case where, whens melt-shaping is film etc., because stretching etc. easily increases the diameter for being formed by gap around particle.In addition, On the basis of resin combination amount of substance, the content of the particle is the range of 0.01 ~ 10 mass %, preferably 0.5 ~ 5.0 mass %.If The smoothness that content is then configured to the formed products after film etc. less than 0.01 mass % is insufficient, and operability is insufficient.On the other hand, In the case where 10 mass %, dispersion of the particle in resin combination is deteriorated, and it is not preferable.It should be noted that by resin group In the case where closing the direct melt-shaping of object and being configured to film etc., the content of particle as described above, it is preferred to for 0.01 ~ 3 mass %, The range of further 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, resin combination high using content, being, for example, 0.5 ~ 10 mass %, being diluted makes It is configured in the resin combination of film etc. the content (in film) and reaches above range.

In turn, as described above, it is desirable that the DBA value of porous silica particle is 200 mMs/kg or less, preferably 100 MM/kg or less.In the case that DBA value is greater than 200 mMs/kg, not only porous silica silicon particle is in resin combination In dispersion be deteriorated, and be also easy to produce gap between resin and particle when being configured to stretched film, it is not preferable.

In addition, as described above, the compression ratio of porous silica silicon particle is preferably 20 ~ 90%, particularly preferably 50 ~ 85% Range.Think that, by making compression ratio within this range, due to the stress being processed into whens stretched film etc., which moderately deforms, make The diameter that gap is formed by around particle reduces.

As described above, the resin combination preferably comprises thermoplasticity noncrystalline resin, especially polyphenylene oxide resin.By resin The direct melt-shaping of composition and in the case where being configured to film etc., on the basis of the quality of resin combination, thermoplasticity amorphous The content ratio of resin is preferably the range of 48 mass % or less, further preferably 5 ~ 48 mass %.Thus, it is possible to make heat resistance It is excellent, and improve dielectric breakdown voltage, it can obtain the stretched film that the dielectric breakdown voltage under high temperature improves.Content is very few In the case where, the improvement effect of heat resistance has the tendency that reduction, and the improvement effect of dielectric breakdown voltage also has becoming for reduction The improvement effect of gesture, draftability is insufficient.From this viewpoint, the content of thermoplasticity noncrystalline resin is more preferably 8 mass % or more, Further preferably 11 mass % or more, particularly preferably 20 mass % or more.In addition, in the case that content is excessive, the crystallization of SPS Property has the tendency that easily reducing, and the heat resistance of film also has the tendency that reduction.From this viewpoint, the content of thermoplasticity noncrystalline resin More preferably 45 mass % or less, further preferably 40 mass % or less, particularly preferably 35 mass % or less.On the other hand, exist Resin combination is used as masterbatch (masterbatch), with gathering without porous silica silicon particle, containing such as syndiotactic structure The masterbatch of the matrix resins such as phenylethylene resin series or other additives carries out using polyphenylene oxide in melting mixing and diluted situation The resin combination that the content ratio of resin is high, such as content is 20 ~ 80 mass %, is diluted the resin for making to be configured to film Content in composition reaches above range.

It, can be in resin without being particularly limited to for the mixed method of above-mentioned porous silica silicon particle and resin material The polymerization stage of material adds, and can also be added to using melting mixing method by polymerizeing in resulting resin material.For example, can Melting mixing is supplied and carried out from the same supply mouth of melting mixing machine by the granular powder and resin material, can also use Resin material is first put into melting mixing machines such as the twin-screw mixer extruders with gas vent, then the particle is added with powder The method at the position melted to the resin material.Wherein, preferably the particle is pre-mixed with resin granular material or toner Afterwards, the method being supplied in the twin-screw mixer extruder with gas vent.According to this method, thus it is speculated that since the particle is attached to tree The surface of fat granule material or toner, therefore when being crushed inside kneading machine, the contact interval of the particle and resin is minimum, So dispersibility further increases.

As the twin-screw mixer extruder with gas vent, it is preferable to use following device: the adding mouth setting of particle is being matched Be placed in the full thread portion of the screw rod inside the twin-screw mixer extruder with gas vent, from above-mentioned adding mouth along screw rod axle center side It is provided at least one downstream with for making particle be kneaded the feeding blade of dispersion and returning to the rotor segment of blade. Herein, gas exhaust piping is used to remove the by-product from resin.In addition, the twin-screw mixer extruder with gas vent preferably 1 ~ There is rotor segment at 3.The mixing dispersion of the particle reduces if scraper plate without spin, if rotor segment is more than resin at 3 Propulsive force is reduced and is easily bent.Additionally, it is preferred that having the kneading disk of the mixing dispersion for supplementing the porous particle.

<capacitor>

The stretched film of aforementioned present invention can be by obtaining capacitor in for example, at least single side lamination metal layer.For gold The material for belonging to layer, is not particularly limited, such as can enumerate aluminium, zinc, nickel, chromium, tin, copper and their alloy.In turn, this A little metal layers can be aoxidized in right amount.In addition, in order to be simply forming metal layer, metal layer is preferably formed using vapour deposition method Vapor deposition type metal layer.It should be noted that when carrying out lamination to metal layer, by presetting coating layer, stretched film can be made Layer (substrate layer) and metal layer have the bonding force of appropriateness, implement metal layer when the processing such as winding in the manufacture of thin film capacitor It will not remove, play the function as capacitor.Make coating layer and metal layer that there is appropriate adhesiveness simultaneously, even if putting Electricity and surface can be small coating layer first removed from film, only metal layer and coating layer is destroyed, and film is not destroyed, Thus without short-circuit condition is caused, the improvement effect of dielectric breakdown voltage can be increased.

Embodiment

Hereinafter, by embodiment, invention is further explained.It should be noted that each characteristic value using following methods into Row measurement.

(1) film thickness

Using electronic gauge (trade name " K-312A type " of Anritsu (strain) system), in the case where needle presses 30g, measurement film is thick Degree.

(2) average grain diameter of particle

(2-1) average grain diameter A

Average grain diameter A in film is as follows: carrying out processing to film surface with plasma reactor exposes particle, benefit Layer is deposited in the gold thin film that the surface forms thickness 200 ~ 300 with golden sputtering equipment.Then, using scanning electron microscope 1 Observed under 10000 times, use Japanese レ ギ ュ レ ー タ ー (strain) LUZEX (ル ー ゼ ッ Network ス processed) 500, for 110 A particle finds out its area equivalent particle size (Di), by wherein measure 5 maximum area equivalent particle sizes (Di) and 5 minimal faces Average grain diameter A of the number mean value of their area equivalent particle size (Di) after except product equivalent particle size (Di) as particle.

(2-2) average grain diameter B

Average grain diameter B before being added in polymer is found out in the following manner.That is, ethyl alcohol is used to be situated between as dispersion Matter is found out averagely using Shimadzu Seisakusho Ltd. laser diffraction formula particle size distribution device SALD-2000J by volume distribution standard Partial size B.

(3) compression ratio of particle

For porous particle before being added in polymer, (most using the micro- compression test MCTM-200 of Shimadzu Seisakusho Ltd.'s system Big load 1gf, minimum load 0.2gf), under conditions of load load speed 0.0725gf/sec, prepare n=5 partial size and The identical particle of average grain diameter, the compression ratio under measuring load 0.2gf, calculates compression ratio of its average value as particle.

(4) content of porous particle, other particles, silicone oil, thermoplasticity noncrystalline resin Y, antioxidant is respectively according to aftermentioned Method measures.

Porous particle, other particles: Selective dissolution resin without dissolved particles solvent, resulting orientation membrane sample is molten Particle is centrifugated by Xie Hou from resin, using particle relative to example weight ratio (weight %) as granule content.Separately Outside, containing in the case where other particles, according to each particle there are ratios to find out respective content.

Silicone oil: pass through¹H-NMR measurement,¹³C-NMR measurement, with integrating number 32 times, using cryoprobe, (high sensitivity is visited Needle) determine silicone oil ingredient and each component amount.

Thermoplasticity noncrystalline resin Y: pass through¹H-NMR measurement,¹³C-NMR measurement, determine thermoplasticity noncrystalline resin Y ingredient and Each component amount.

Antioxidant: pass through¹H-NMR measurement,¹³C-NMR measurement, determine antioxidant ingredient and each component amount.It should Illustrate, in N, bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) the propionamide] (registered trademarks of N '-hexane -1,6- diyl Irg1098 in the case where), to peak intensity caused by the hydrogen in the hydrocarbon chain between tert-butyl-hydroxy phenyl and amido bond Degree is measured.Based on the NMR measurement result, the content of former stabilizer is converted into when finding out stabilizer and resin reaction.In addition, It is mixed not with the stabilizer of polymer reaction and with the stabilizer of polymer reaction, even if being conceived to same hydrocarbon chain In the case where also detecting that multiple peak positions, content is found out according to their aggregate value.

(5) it is film-made draftability

Under conditions of each embodiment and comparative example, polymer is supplied to extruder, according to following standard, to passing through mold (ダ イ ス) and the generation situation of volatile ingredient when carrying out melting extrusion and the film system of film stretched in film making process Film property is evaluated,

◎: without coarse agglutinator etc. when polymer melting squeezes out, film making process without fracture, can also be produced；

〇: there is coarse agglutinator when squeezing out in polymer melting, but without fracture, can be produced；

△: there is coarse agglutinator when squeezing out in polymer melting, and is broken once in a while, can not carry out steady production；

×: coarse agglutinator is obvious when polymer melting squeezes out, or is broken frequent occurrence, can not be produced.

(6) filter boosts

Using Japanese PALL corporation H-250 (sintering (grain) type filters that 25 μm of mesh), it will include small porous particle A's Resin is converted into discharge rate (kg)/filter area (cm²) when, in 300 DEG C of extrusion temperature, 5kg/cm²In the case where lower filtering, The filter differential pressures (Δ P: unit MPa) begun to ramp up from initial pressure when having filtered 100kg are evaluated, according to subscript Standard is evaluated,

◎: filter, can steadily extrusion resin without boosting when polymer melting squeezes out；

〇: filter temporarily boosts when polymer melting squeezes out, but can steadily extrusion resin；

△: the pressure of filter slowly rises when polymer melting squeezes out, can not extrusion resin steadily in the long term；

×: the pressure of filter steeply rises when polymer melting squeezes out, and extrusion resin is unable in the short time.

(7) refractive index of thickness direction

The Abbe refractometer with sodium D-line (589nm) for light source is used, the refraction of thickness direction is measured at 23 DEG C, 65%RH Rate (Nz).The refractive index of thickness direction is higher to mean that strand is orientated along film surface direction.

(8) coarse agglutinating particle number

For film sample, using universal projector, amplify 20 times using transillumination, to 1m²Have contained in area There is the granule number of 25 μm or more maximum lengths to be counted.

(9) voidage

Film through-thickness and width direction are cut off with slicer, for section, (strain) Hitachi's system is used to scan electricity Sub- microscope S-4700 observes the porous silica silicon particle on section in film and the sky around them under 20000 times Gap finds out the diameter of the section of each particle and the film surface direction of each circumgranular gap section, presses for 10 particles The voidage of each particle is calculated according to following formula；

Voidage=((circumgranular aperture diameter-partial size)/circumgranular aperture diameter) × 100

For 10 particles, the average value of voidage is calculated as average void fraction, is evaluated substantially free in film Gap or substantial tight；

〇: substantial tight (average void fraction is 30% or less)

△: substantial tight (average void fraction is greater than 30% and is 50% or less)

×: substantially there is gap (average void fraction is greater than 50%).

(10) surface roughness (Ra and Rz)

Using non-contact 3-D roughmeter (small slope studies made, ET-30HK), swashed with the semiconductor of wavelength 780nm Light, 1.6 μm of beam diameter of light contact pilotage, in measured length (Lx) 1mm, 2 μm of sampling interval, cutter size (cut-off) 100 0.25mm, 10,000 times of thickness direction enlargement ratio, 200 times of horizontal magnification multiplying power, number of scanning lines (therefore, measurements of Y-direction Length Ly=0.2mm) under conditions of measure film surface protrusion distribution.It, will when indicating the roughness curved surface with Z=f (x, y) Centerline average surface roughness (Ra, unit: nm) by the resulting value of following formula as film.

[mathematical expression 1]

。

In addition, by the resulting film surface of above-mentioned Ra protrusion distribution in, from the higher position of peak (Hp) take 5 points and It takes at 5 points from the lower of paddy (Hv), finds out 10 mean roughness (Rz, unit: nm) according to the following formula.

[mathematical expression 2]

。

(11) windability

In the manufacturing process of film, film is rolled up to the volume of 6000m with 550mm width, 100m/ minutes speed Shape is rolled situation, the appearance of volume according to it, is evaluated according to following standard；

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

B: due to the influence of the coarse agglutinating particle in film, there is 1 pimple more than and less than 5 in the surface of volume (convex protuberance), substantially well

C: there are many coarse agglutinator quantity in film, and 5 or more pimples (convex protuberance), appearance occurs in the surface of volume It is bad

D: the film end face offset rolled up, winding form are bad.

(12) dielectric breakdown voltage (BDV) and deviation

Using resulting Biaxially oriented film (stretching membrane sample), according to what is recorded in Japanese Industrial Standards JIS specification C2151 Plate electrode method in DC test is carried out using the electric Co. Ltd. system ITS-6003 of Tokyo essence with the rate of rise of 0.1kV/sec Measurement, voltage when puncturing is measured as dielectric breakdown voltage.Measurement carries out n=50 times, and average value is dielectric breakdown Voltage, standard deviation are the deviation of dielectric breakdown voltage.It should be noted that at room temperature progress of the measurement at 25 DEG C.

(13) resistance to scraping

Film is cut into 1/2 inch of width, length 400mm along its length, makes to cut using film nigration machine Film moves in stainless steel guide pin (surface roughness: Ra 40nm), with movement speed 20mm/ seconds round-trip 200mm away from From (90 ° of circumvolution angle, outlet side tension 50g) twice.After movement, with Hitachi scanning electron microscope S-4700 at 100 times Under, the adhesion amount of the guide pin contact surface in film contacts portion and film for guide pin observation particle, according to following standard into Row determines.The accumulation width of the particle of scraping is smaller, and resistance to scraping is more excellent,

〇: less than 0.20mm

△: 0.20mm more than and less than 0.50mm

×: 0.50mm or more.

(14) resistance to blocking

Film is cut into the square of side length 100mm, the film cut overlapping is made into 20 μm of overall thickness or more (single sheet of thin Film with a thickness of using 1 at 20 μm or more), be made with the aluminium foil of identical size each 1 laminated body clipped up and down.Use hot pressing Machine is thermally compressed the laminated body.Crimping condition is 125 DEG C of pressed temperature, moulding pressure 5MPa, pressing time 30 minutes.Pressure It after connecing, will carry out being heat-treated for 30 minutes at laminated body in an oven 150 DEG C, measure the film and aluminium foil of laminated body after cooling Peeling force.The measurement of peeling force uses cupping machine, is measured under conditions of tensile speed 300mm/min, according to survey Determine result according to following standard determination adhesive,

〇: almost removing naturally or Average peel force is 1.0mN/mm or less；

△: focal adhesion, but Average peel force is greater than 1.0mN/mm and is 3.0mN/mm or less；

×: whole adhesions, Average peel force are greater than 3.0mN/mm.

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

Sample 250mg at 105 DEG C of precision weighing after drying 2 hours, is added the 1/500N-DBA solution of 50ml thereto (petroleum ether solvent) is placed 2 hours at 20 DEG C.Chloroform 5ml is added into its supernatant 25ml, crystal violet indicator 2 ~ 3 drips, use 1/100N- perchloric acid solution (acetic anhydride solvent), which is titrated to purple, becomes blue, and titration value at this time is as Aml.It is additionally carried out Blank test calculates DBA value as Bml according to the following formula,

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

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

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

[embodiment 1]

(the silicone oil attachment of porous silica silicon particle is handled)

For porous silica silicon particle, (average grain diameter=2.7 μm, pore volume=1.5ml/g, are averaged at compression ratio=66% Aperture=10nm) 100 mass parts, with spraying spraying silicone oil (SHIN-ETSU HANTOTAI's シ リ コ ー Application system, linear dimethyl polysiloxane, KF-96- 100CS) 1 mass parts are then placed in mixing machine and are stirred.

(processing of the melting mixing of resin material and porous silica silicon particle)

The double-screw mixing with gas vent is made using Kobe Steel's (strain) at resin input port and 2 with vacuum vent holes It is provided with the feeding blade of rotor disk at 2 (rotor disk) on refining extruder KTX-46 and returns to blade and then is rotating The downstream side of scraping plate part is configured with configured with kneading disk, in the downstream side of kneading disk with reversed transmission full thread spiral shell The equipment of the resistance portion of bar.By resin input port, using 30 mass parts as poly- (2, the 6- dimethyl-of thermoplasticity noncrystalline resin Y Isosorbide-5-Nitrae-phenylene) ether (intrinsic viscosity measured in chloroform is 0.32dl/g, glass transition temperature is 210 DEG C) and 70 mass Part is 3.0 × 10 as the weight average molecular weight of polystyrene resin⁵And it uses¹³C-NMR measurement is advised between observing almost The polystyrene of structure, the 0.1 mass parts above-mentioned porous silica silicon particle that is attached with silicone oil total relative to these resins, 2 Pentaerythrite four [3- (3,5- di-tert-butyl-hydroxy phenyl) the propionic ester] (Ciba of mass parts as antioxidant (C1) Specialty Chemicals corporation: trade name IRGANOX1010,120 DEG C of fusing point, 335 DEG C of pyrolysis temperature) press above-mentioned ratio Example mixing dispersion forms mixture, which is put into 35 mass parts/Hr feed speed from resin input port, with machine barrel 270 DEG C of temperature, screw speed 250rpm are by die hole melting extrusion at item (strand) shape.Then, with cooling bath that resin is cooling Afterwards, it is cut with pelleter, obtains the resin combination fragment of major diameter about 4mm, minor axis about 4mm, length about 3mm.

(films of alignment films)

Resulting resin combination is 7 hours dry at 120 DEG C, it is then fed into extruder, is carried out at 300 DEG C Melting is cooled and solidified on the curtain coating drum (casting drum) for being cooled to 50 DEG C, is made after die slot (die slit) extrusion Non-stretched.

By this non-stretched, (mechanical axis direction) stretches 3.5 times, after being then directed into stenter along longitudinal direction at 140 DEG C, edge Laterally (direction vertical with mechanical axis direction and thickness direction) stretches 4.5 times.At this point, stretched portion is divided into 4 regions, Cross directional stretch speed is 5000%/minute.In addition, temperature stretching in the transverse direction 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, 9 seconds heat fixations are carried out at 250 DEG C, and then in the phase for being cooled to 180 DEG C Between transversely carry out 2% relaxation processes, obtain 2.5 μm of thickness Biaxially oriented film and wound into rolls.The characteristic of gained film is shown In table 1.

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

Other than changing according to the record of table 1 ~ 3, operation similarly to Example 1 is repeated.Embodiment institute Alignment films evaluation result is shown in table 1 and 2, alignment films obtained by comparative example evaluation result is shown in table in 3.

[table 1]

。

[table 2]

。

[table 3]

。

Porous silica in table 1 ~ 3 refers to that porous silica silicon particle, spherical organic silicon refer to cross-linked silicone tree Rouge particle, non-porous silica refer to spherical silica particles.Irg1010 in table 1 refer to pentaerythrite four [3- (3, 5- di-tert-butyl-hydroxy phenyl) propionic ester] (Ciba Specialty Chemicals corporation: trade name IRGANOX1010), Irg1098 refers to N, the bis- 3- of N '-(3 ' 5 '-di-t-butyls -4 '-hydroxy phenyl) propiono hexa-methylene two Amine (Ciba Specialty Chemicals corporation: trade name IRGANOX1098), Irg565 refer to bis- (the just pungent sulphur of 2,4- Base) -6- (4 '-hydroxyl -3,5- di-tert-butyl amido) -1,3,5- triazine (Ciba Specialty Chemicals corporation: Trade name IRGANOX565).PPE in table 1 and 2 refers to that poly- (2,6- dimethyl -1,4- phenylene) (what is measured in chloroform consolidates ether Having viscosity is 0.32dl/g, glass transition temperature is 210 DEG C), PC refer to bisphenol A polycarbonate (light petrochemistry system out, Light polycarbonate A300, glass transition temperature are 145 DEG C out).In addition, in average grain diameter column in table 3 in film, "-※ " Refer to that the agglutination of particle is more, stops the measurement of average grain diameter.

[synthesis example 1]

The sodium silicate aqueous solution of 22wt% is reacted with the aqueous sulfuric acid of 37wt% using mixing nozzle, obtains silica The hydrosol.Silica hydrosol is subjected to gelation in about 7 minutes, obtains silica hydrogel.By the silica water-setting After glue coarse powder is broken to diameter about 10mm, 5 hours hydro-thermal process are carried out under conditions of 90 DEG C, pH9.0, are then washed.Then, into The 1st process of row, that is, it uses vibrated fluidized bed (central chemical industry machine corporation, trade name " vibrational fluidized bed device VUA-15 type "), Silica hydrogel after washing is 60 minutes dry, obtain the dry silica to water content 7%.Then, the 2nd is carried out Process, that is, add water in Xiang Jinhang dry silica, be adjusted to the silica of water content 37%.Then it carries out 3rd process, that is, use vibra fluidized bed drying 2 hours again, obtain the gelation silica of water content 1%.Use air-flow powder Broken machine carries out pulverization process to the silica after the drying, and resulting silica 1 is added in vibrated fluidized bed for 00 part, Lateral dominance dehumidifying after air carries out vibratory liquefaction side be sprayed 12 parts of n-octytriethoxysilane carry out fluidize mix 30 minutes. Then, it is put into rapidly in the constant temperature and humidity cabinet for keeping 25 DEG C of temperature, humidity 90%, is kept for 72 hours two after being surface-treated Silica powder.Again, airslide disintegrating mill is used to carry out pulverization process in order to disperse silica.Gained silicon dioxide powder The characteristic value of body 1 (porous silica silicon particle 1) is shown in Table 4.

[synthesis example 2,3,5]

It other than adjusting average grain diameter, carries out similarly handling with synthesis example 1 in addition to changing airslide disintegrating mill condition.Gained The characteristic value of silicon-dioxide powdery 2,3,5 is shown in Table 4.

[synthesis example 4]

Other than changing added n-octytriethoxysilane amount, similarly handle with synthesis example 1.Gained The characteristic value of silicon-dioxide powdery 4 is shown in Table 4.

[synthesis example 6]

In order to which small particle is made, after the processing of first time airslide disintegrating mill, 10% slurry is made in silica with distilled water Material increases the case of wet attrition process that (DYNO-MILL, capacity 5L) is sanded, and in addition to this carries out similarly handling with synthesis example 1. The characteristic value of gained silicon-dioxide powdery 6 is shown in Table 4.If the too small silicon-dioxide powdery average grain diameter is 0.3 μm, can not Measure compression ratio.

[synthesis example 7]

Other than the surface treatment of not firm application n-octytriethoxysilane, similarly handle with synthesis example 1. The characteristic value of gained silicon-dioxide powdery 7 is shown in Table 4.

[reference example 1]

The double-screw mixing with gas vent is made using Kobe Steel's (strain) at resin input port and 2 with vacuum vent holes Be provided with the feeding blade of rotor disk at 2 on refining extruder KTX-46 and return blade so that rotor segment portion close to Downstream side is configured with the resistance portion with reversed transmission full flight screw configured with kneading disk, in the downstream side of kneading disk Equipment.Mitsubishi work of 40 mass parts of investment as polyphenylene oxide resin (hereinafter sometimes referred to simply as PPE) is mixed from resin input port Engineering plastics Iupiace PX-100L (Tg210 DEG C), 55.8 mass parts are (following as the polystyrene resin of syndiotactic structure Sometimes referred to simply as SPS) go out that light is emerging to produce XAREC 60ZC processed, Ciba Specialty of 0.2 mass parts as antioxidant Chemicals corporation IRGANOX 1010.

In turn, 4 mass parts are added as more from the middle section of twin-screw mixer extruder (downstream part of kneading disk) The above-mentioned silicon-dioxide powdery 1 of hole silica dioxide granule, carries out mixing dispersion.At this point, with mixture supply amount be 35 mass parts/ Hr, 270 DEG C of barrel temperature, screw speed 250rpm, into strips by die hole melting extrusion.Then, with cooling bath that resin is cooling Afterwards, it is cut with pelleter, obtains the resin combination fragment of major diameter about 4mm, minor axis about 4mm, length about 3mm.It is resulting Resin combination fragment is shown in Table 4.

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

The use ratio of porous silica silicon particle, PPE, SPS used according to table 3 record, in addition to this with reference Example 1 is similarly obtained resin combination fragment.It is shown in Table 4 together.

[reference example 6]

Other than porous silica silicon particle, the spherical organic silicon resin particle 4 for the use of average grain diameter B being also 0.3 μm In addition to this mass parts, the use ratio of SPS are similarly obtained resin combination fragment with reference example 1 according to the record of table 1.One And it is shown in Table 4.

[referring to comparative example 4]

Porous silica used is replaced by 2.0 μm of spherical silica particles (non-porous) using average grain diameter B In addition to this silicon particle is similarly obtained resin combination fragment with reference example 1.It is shown in Table 4 together.

[table 4]

。

[embodiment 21]

By resin combination fragment (master batch chips A), polyphenylene oxide resin (Mitsubishi Engineering-Plastics system obtained in reference example 1 Iupiace PX-100L), the polystyrene resin of syndiotactic structure (light is emerging out produces XAREC 60ZC processed), in polyphenylene oxide resin Contain 5 weight % Ciba Specialty as antioxidant in (Mitsubishi Engineering-Plastics Iupiace PX-100L) After the master batch chips of Chemicals corporation IRGANOX 1010 are separately dried, to obtain the ratio of the film formed recorded in table 5 They are mixed and are supplied in extruder by example, are melted at 300 DEG C, after die slot extrusion, are being cooled to 50 DEG C of curtain coating drum On cooled and solidified, be made non-stretched.It should be noted that since swarming dissipates antioxidant in the middle part of the film-forming process of film, Therefore the oxidation preventive content in raw mixture is adjusted to slightly volume, so that the content of antioxidant in the film reaches 1 weight Measure %.

By this non-stretched, (mechanical axis direction) stretches 3.5 times, after being then directed into stenter along longitudinal direction at 140 DEG C, edge Laterally (direction vertical with mechanical axis direction and thickness direction) stretches 4.5 times.At this point, lateral tensile speed be 5000%/point Clock, temperature stretching in the transverse direction are 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, 9 seconds heat fixations are carried out at 250 DEG C, and then transversely carry out 2% relaxation processes during being cooled to 180 DEG C, obtain thickness The Biaxially oriented film and wound into rolls of 2.5 μm of degree.The characteristic of gained 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 documented by table 5 ~ 7, by polyphenylene oxide resin, polycarbonate resin, syndiotactic structure polyphenyl Vinylite and master batch chips containing antioxidant are used in combination, so that the group of gained film becomes shown in the record of table 5 ~ 7, In addition to this repeat operation similarly to Example 21.Gained stretched film evaluation result is shown in table in 5 ~ 7.It should say It is bright, in embodiment 25,26, as the master batch chips containing antioxidant, tied using containing rule between 5 weight % IRGANOX 1010 The polystyrene resin of structure (light is emerging out produces 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 particle and antioxidant with Reference example 1 is equally mixed, so that as shown in the record of table 5 ~ 7, it is broken to obtain resin combination first for the composition of gained film Piece.Gained resin combination is dry, it is filmed to obtain biaxially-stretched film similarly to Example 21.The evaluation of gained stretched film As a result it is shown in table 5 ~ 7.

[table 5]

。

[table 6]

。

[table 7]

。

PC in table 5 ~ 7 is that (light petrochemistry produces light polycarbonate A300 to bisphenol A polycarbonate out, vitrifying turns Temperature is 145 DEG C).

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

Industrial applicability

The alignment films of the invention for first, resistance to scraping and windability excellent, therefore can be especially suitable for thin-film capacitor The basement membrane of device.

In addition, the stretched film of the invention for second, the dispersibility of particle aperture diameter that is excellent, and being generated by particle It is small, therefore resistance to scraping, operability, dielectric breakdown characteristic (dielectric breakdown voltage and its deviation) are excellent, may be particularly useful for film Capacitor is used.

Claims (13)

1. stretched film, which is characterized in that the stretched film includes resin combination, which contains the benzene second of syndiotactic structure The porous particle that alkene based polymer and average grain diameter are 0.5 ~ 5.0 μm, on the basis of the quality of the resin combination, porous particle Content be 0.01 mass % or more and 3 mass % ranges below,

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

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

(2) porous particle be average grain diameter A be 0.5 ~ 5 μm, DBA value is 200 mMs/kg porous silica below Grain.

2. stretched film according to claim 1, which includes resin combination, which advises knot between containing The styrenic of structure, the porous particle and silicone oil that average grain diameter is 0.5 ~ 5.0 μm,

On the basis of the quality of the resin combination, the content of porous particle is 0.01 mass % or more and 3 mass % models below It encloses,

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

3. stretched film according to claim 1, which includes resin combination, which advises knot between containing The polystyrene resin and average grain diameter A of structure are 0.5 ~ 5 μm, DBA value is 200 mMs/kg porous silica below Silicon particle,

On the basis of resin combination amount of substance, the content of the porous silica silicon particle 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 relative to the quality of film, containing 5 mass % with Upper and 48 mass % thermoplasticity noncrystalline resin below.

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

7. stretched film according to any one of claim 1 to 3, wherein relative to the quality of film, contain 0.1 mass % Above and 5 mass % antioxidants below.

8. stretched film according to claim 7, wherein the pyrolysis temperature of the antioxidant is 250 DEG C or more.

9. stretched film according to any one of claim 1 to 3, wherein porous particle or porous silica silicon particle The range that compression ratio is 20 ~ 90%.

10. stretched film according to any one of claim 1 to 3, wherein the stretched film is with 0.01 mass % or more and 3 It is 0.01 μm of particle more than and less than 0.5 μm that quality % range below, which contains average grain diameter,.

11. stretched film according to any one of claim 1 to 3, wherein 25 μm of maximum length or more contained in film Coarse agglutinating particle quantity be 10/m²Below.

12. stretched film according to any one of claim 1 to 3, wherein porous particle or porous contained in film The voidage that generated following formula (1) indicates around silica dioxide granule is 50% or less:

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

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

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