CN1703459A - Thermoplastic saturated norbornene based resin film, ans method for producing thermoplastic saturated norbornene based resin film - Google Patents

Abstract

It is an object of the invention to provide a thermoplastic saturated norbornene resin film, an optical film, a protective film for a polarizer, a retardation film, a polarizing plate obtainable by this, which realizes the compatibility between excellent physical properties and optical characteristics, and a method of producing a thermoplastic saturated norbornene resin film. The invention relates to a thermoplastic saturated norbornene resin film, which is obtainable by using a thermoplastic saturated norbornene resin composition containing a thermoplastic saturated norbornene resin in an amount of 100 parts by weight and a rubber polymer in an amount of 5 to 40 parts by weight, parallel transmittance being 87% or more.

Description

Thermoplasticity saturated norbornene resin film and manufacture method thereof

Technical field

The present invention relates to have concurrently the manufacture method of thermoplasticity saturated norbornene resin film, blooming, polarizer protecting film, phase difference film, polaroid and the thermoplasticity saturated norbornene resin film of high physical property and optical characteristics.

Background technology

Thermoplasticity saturated norbornene resinoid has excellent performance at aspects such as thermotolerance, optical characteristics, the transparency, electrical specifications, for studying as the application of the film that is used for auto parts, electric-electronic component, optical element and building materials etc.Especially expect its polarizer protecting film, the application of phase difference film as the polaroid of the liquid crystal indicator that is used for desk top computer, Die elektrische Zeituhr, word processor, automobile, mechanical counter class etc.

Polaroid is usually by in the polyvinyl alcohol resin that makes after iodine or dichroic dye are adsorbed in stretch orientation and the polarizer that forms, bonding polarizer protecting film constitutes on the two sides of polarizer.For as the blooming of polarizer protecting film, require optical characteristics excellences such as photopermeability, have and can prevent the pyritous thermotolerance that applies in mechanical strength that the big polarizer of shrinkability shrinks and the ability manufacturing process etc.

In the past, as polarizer protecting film, the blooming that always uses tri acetyl cellulose to constitute.But; though the blooming that is made of tri acetyl cellulose has high optical characteristics; but thermotolerance, wet fastness deficiency; when under high temperature or high humidity atmosphere, using for a long time; exist to produce the peeling off of remarkable reduction, polarizer and protective membrane of degree of polarization, because the hydrolysis of tri acetyl cellulose produces the reduction of the transparency etc., make the problem of the performance reduction of polaroid.

In addition, be purpose with the deflection that compensates by the liquid crystal material time, in polaroid, use phase difference film.As this phase difference film, use the phase difference film that constitutes by polycarbonate resin, polysulfone resin resin transparent like this, excellent heat resistance.

Te Kaiping 5-247324 communique discloses the blooming that is made of thermoplasticity saturated norbornene resinoid.The blooming that is made of thermoplasticity saturated norbornene resinoid demonstrates excellent thermotolerance except for the excellent optical such as the little feature of the double refraction performance of stress, high transparent.Therefore, if use the blooming that constitutes by thermoplasticity saturated norbornene resinoid, the polaroid that can expect to obtain having high optical characteristics.

But the blooming that is made of thermoplasticity saturated norbornene resinoid exists and is highly brittle, the problem of filming difficulty.In addition, even want to use the extrusion moulding manufactured, if draw speed is soon then film fracture, therefore also existing problems on productivity.

In addition, carry out the operation of applying polaroid on liquid crystal cells in the manufacturing of liquid crystal indicator, be involved in bubble, foreign matter during applying, perhaps to have defective be inevitable to polaroid self.Therefore, after the operation that polaroid is fitted to liquid crystal cells, check, carry out when having defective polaroid is peeled off, the operation that the what is called utilized again of liquid crystal cells of high price is utilized once more.For being utilized again, this becomes possibility; must be able to easily polaroid be peeled off when peeling off; but, also exist and produce fracture, the problem of usability difference once more when peeling off for having used the polarizer protecting film that constitutes by crisp thermoplasticity saturated norbornene resinoid, the polaroid of phase difference film.

To this, the spy opens flat 3-106963 communique and discloses the resin combination that contains norbornene open-loop polymkeric substance hydride and rubber.It is by adding rubber in norbornene open-loop polymkeric substance hydride, obtains ftractureing when being used for the inside moulding of metal parts and moulding product that the contraction during moulding is inhibited, in addition, excellent in adhesion with thermoplasticity saturated norbornene base polymer.This resin combination is considered to the physical propertys such as fragility that norbornene resin has and improves.But by the interpolation of rubber, optical characteristics such as parallel rays transmitance significantly reduce, and can not be used as blooming.

In addition, put down in writing in the Te Kaiping 5-247324 communique by thermoplasticity saturated norbornene resinoid with the Synergist S-421 95 of its non-conforming and constituted, Synergist S-421 95 forms microdomain and dispersive thermoplasticity saturated norbornene based resin composition and by its optical material that constitutes, when using rubber polymer as Synergist S-421 95, the purport that accesses improvement with the adhesiveproperties of various coating and film is disclosed.But, in order to obtain sufficient optical property, the amount of the rubber polymer that adds is about 0.001～0.8 weight part with respect to thermoplasticity saturated norbornene resinoid 100 weight parts, adds Synergist S-421 95 with this degree, can not realize the improvement of sufficient physical property.

In addition, in No. 2940014 communique of special permission, disclose the thermoplastic resin composition who constitutes by thermoplasticity saturated norbornene resin and rubber polymer, put down in writing the formed body that this thermoplastic resin composition's injection molding is formed.But, though in No. 2940014 communique of special permission, the shock-resistance of the formed body made and total light transmittance etc. are put down in writing, but for the manufacturing of blooming without any record, for as the integral parallel rays transmitance of the performance of blooming, mist degree also without any record.

In addition, the spy opens to disclose in the flat 5-148413 communique thermoplasticity saturated norbornene resin and rubber constituent is dissolved or dispersed in the solvent, the film that adopts casting method to form.It has improved degree of stretching for thermoplasticity saturated norbornene resin-filled rubber composition.But optical characteristics such as the parallel rays transmitance of the film of manufacturing can not be used as blooming.

Summary of the invention

The present invention is in view of above-mentioned present situation, and purpose is to provide the manufacture method of the thermoplasticity saturated norbornene resin film, blooming, polarizer protecting film, phase difference film, polaroid and the thermoplasticity saturated norbornene resin film that have high physical property and optical characteristics simultaneously.

The present invention the 1st relates to thermoplasticity saturated norbornene resin film, this thermoplasticity saturated norbornene resin film use contains the thermoplasticity saturated norbornene based resin composition of thermoplasticity saturated norbornene resinoid 100 weight parts and rubber polymer 5～40 weight parts and forms, and the parallel rays transmitance is more than 87%.

The difference of above-mentioned thermoplasticity saturated norbornene resinoid and above-mentioned rubber polymer preferred index is below 0.2.

The present invention the 1st the preferred modulus in tension of thermoplasticity saturated norbornene resin film is more than the 900MPa, and tension fracture elongation rate is 4～40%, preferred residual phase difference is below the 3nm, and optical axis deviation is below ± 10 ° with respect to long axis direction, and more preferably the residual phase difference is below the 1nm.In addition, the maximum value when preferred employing is measured thickness according to the method for JIS K 7130 and the difference of minimum value are below the 5 μ m, preferably can batch under the situation that does not make its fracture with tension force 500N/650mm.

Above-mentioned rubber polymer is preferably the styrenic elastomerics, and above-mentioned styrenic elastomerics is preferably styrene-ethylene-butylene copolymer of vinylbenzene composition 25～50 weight %, ethene composition 25～50 weight %.

Above-mentioned thermoplasticity saturated norbornene resin combination preferably also contains the thermoplastic resin of number-average molecular weight 300～10,000.

The present invention the 1st thermoplasticity saturated norbornene resin film preferred light coefficient of elasticity is 2.0 * 10 ^-11Pa ^-1Below.

The blooming, polarizer protecting film and the phase difference film that are made of the present invention the 1st thermoplasticity saturated norbornene resin film also are one of the present invention.

The present invention the 2nd relates to polaroid; it is made of polarizer protecting film and the polarizer that the norbornene resin composition constitutes; wherein; the parallel rays transmitance is more than 40%; under condition, with draw speed 300mm/min, not fracture when tension force 2.5～3N/25mm peels off according to 180 ° of stripping tests of JIS Z 1528.

It is below 2% that the present invention the 2nd polaroid preferably carries out 90 ℃, the 24 hours size changing rates before and after the heating.

Direct stacked the phase difference film of the present invention and polaroid that forms also is one of the present invention on the single face at least of polarizer.

The manufacture method of thermoplasticity saturated norbornene resin film also is one of the present invention, it is for adopting the method for the thermoplasticity saturated norbornene resin film that melt extrudes manufactured the present invention the 1st, wherein, with the melt temperature of thermoplasticity saturated norbornene based resin composition fusion up to the thermoplasticity saturated norbornene based resin composition of sending into punch die, be the resinoid second-order transition temperature of thermoplasticity saturated norbornene+below 135 ℃, and will be below 40 minutes up to the average retention time of sending into punch die after the fusion of thermoplasticity saturated norbornene based resin composition.

In the manufacture method of thermoplasticity saturated norbornene resin film of the present invention, the preferred temperature before the contacting of the thermoplasticity saturated norbornene based resin composition of extruding from punch die with cooling roller, be the resinoid second-order transition temperature of thermoplasticity saturated norbornene+more than 50 ℃, more preferably the resinoid second-order transition temperature of thermoplasticity saturated norbornene+more than 80 ℃.

Description of drawings

Fig. 1 is the mode chart of 1 example of infiltration type electron micrograph picture in cross section of expression the present invention's the 1st thermoplasticity saturated norbornene resin film.

Fig. 2 is the mode chart of 1 example of infiltration type electron micrograph picture of representing the cross section of thermoplasticity saturated norbornene resin film in the past.

Fig. 3 is the infiltration type electron micrograph picture in the cross section of the thermoplasticity saturated norbornene resin film of making among the embodiment 1.

Among the figure, 1 expression thermoplasticity saturated norbornene resinoid, 2 expression rubber polymers.

Embodiment

Below the present invention is described in detail.

The present invention the 1st thermoplasticity saturated norbornene resin film (below be also referred to as the TPSNB resin film) uses the thermoplasticity saturated norbornene based resin composition that contains thermoplasticity saturated norbornene resinoid (below be also referred to as the TPSNB resinoid) and rubber polymer (below be also referred to as the TPSNB based resin composition) and forms.

So-called in this manual TPSNB resinoid, be meant norbornylene class polymer of monomers or norborneol vinyl monomer and can with the monomeric multipolymer of its copolymerization, mean that intramolecularly does not have unsaturated link(age) or when intramolecularly has unsaturated link(age) with its hydrogenation.

Be not particularly limited as above-mentioned norbornene polymer, for example, preferably use polymkeric substance that at least a kind of norbornylene class monomer polymerization shown in the following general formula (1) is obtained or with at least a kind of norborneol vinyl monomer shown in the following general formula (1) and the polymkeric substance that can form with the co-polymerized monomer copolymerization of its copolymerization.

In the formula, A, B represent the alkyl of hydrogen atom or carbon number 1～10 independently, and X, Y represent hydrogen atom, halogen atom or organic group independently, and m represents 0 or 1.

Be not particularly limited as the norborneol vinyl monomer shown in the above-mentioned general formula (1), preferred use does not for example have dicyclo [2.2.1]-2-heptene, three ring [5.2.1.0 ^2,6]-8-decene, three ring [5.2.1.0 ^2,6]-3-decene, three ring [6.2.1.0 ^1,9]-9-undecylene, three ring [6.2.1.0 ^1,9]-4-undecylene, Fourth Ring [4.4.0.1 ^2,5.1 ^7,10The monomer of functional groups such as]-3-dodecylene; Has 8-methoxycarbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecylene, 8-methyl-8-methoxycarbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10The monomer of]-3-dodecylene, 5-methoxycarbonyl dicyclo [2.2.1]-functional groups such as 2-heptene.Wherein, from making the aspect of the high polymkeric substance of second-order transition temperature, m is 1 tetracyclododecane derivative in the preferred above-mentioned general formula (1).These norborneol vinyl monomers may be used alone, two or more kinds can also be used.

Can be not particularly limited with the co-polymerized monomer of the norbornylene class monomer copolymerization shown in the above-mentioned general formula (1), can enumerate the norborneol vinyl monomer that does not contain in for example above-mentioned general formula (1), the cyclic olefin monomer that does not have the norbornylene skeleton.As the norborneol vinyl monomer that does not contain in the above-mentioned general formula (1), can enumerate for example five rings [6.5.1.1 ^3,6.0 ^2,7.0 ^9,13]-4-15 carbenes, five rings [6.6.1.1 ^3,6.0 ^2,7.0 ^9,14]-4-cetene, five rings [6.5.1.1 ^3,6.0 ^2,7.0 ^9,13]-11-15 carbenes, dicyclopentadiene, five rings [6.5.1.1 ^3,6.0 ^2,7.0 ^9,13]-15 carbon-4, many cyclenes such as 11-diene etc.

As the above-mentioned cyclic olefin monomer that does not have the norbornylene skeleton, there is no particular restriction, can enumerate for example cyclopentenes, cyclooctene, 1,5-cyclooctadiene, 1,5, cyclenes hydro carbons such as 9-cyclododecatriene etc.

As the norbornylene class monomer methods shown in the above-mentioned general formula of polymerization (1) or make the norborneol vinyl monomer shown in the above-mentioned general formula (1) and can be not particularly limited, can use known method in the past such as for example open loop metathesis polymerizable, addition polymerization etc. with the method for the co-polymerized monomer copolymerization of its copolymerization.

Be not particularly limited as method, can enumerate the method etc. of known catalyzer in the past such as for example Wilkinson complex compound, Cobaltous diacetate/triethyl aluminum, acetylacetonate nickel/triisobutyl aluminium, palladium-carbon, ruthenium complex, ruthenium-carbon, nickel-diatomite etc. of using above-mentioned norbornene polymer or norbornylene analog copolymer hydrogenation.In addition, when when polymerization, using ruthenium alkylidene complex compound, ruthenium vinylidene base complex, ruthenium Fischer sylvestrene complex compound etc. to show the complex compound of metathesis polymerizable, can under the situation that does not add hydrogenation catalyst, carry out hydrogenation, carry out polymerization and hydrogenant operation continuously by the hydrogen pressurization.

Above-mentioned hydrogenation because of the kind of catalyzer at homogeneous system or heterodisperse system, under the hydrogen-pressure of common 1～200 air pressure, carry out under 0～250 ℃ the condition.

So-called above-mentioned TPSNB resinoid, when above-mentioned norbornene polymer or above-mentioned norbornylene analog copolymer when intramolecularly has unsaturated link(age), mean that carrying out hydrogenation reaches more than 50% hydrogenation ratio at least, preferred hydrogenation ratio is more than 90%, more preferably more than 99%.If hydrogenation ratio less than 50%, photostabilization, the heat-resisting degradation property of the present invention's the 1st of manufacturing TPSNB resin film are poor.

The number-average molecular weight of the resinoid employing polystyrene conversion of above-mentioned TPSNB is preferably 10,000～1,000,000.If less than 10,000, the mechanical strength of the present invention's the 1st of manufacturing TPSNB resin film are not enough sometimes, if surpass 1,000,000, melt molding significantly reduces sometimes.More preferably 10,000 5000～700,000.

Even also obtain institute's phase effect easily from the use level that reduces rubber polymer, in the scope that satisfies other important documents such as melt molding, preferably use more high-molecular weight TPSNB resinoid.

The resinoid second-order transition temperature of above-mentioned TPSNB is preferably 70～180 ℃.If 70 ℃ of less thaies, the poor heat resistance of the present invention's the 1st of Zhi Zaoing TPSNB resin film sometimes, if surpass 180 ℃, the difficulty that becomes of moulding sometimes.

Above-mentioned TPSNB based resin composition contains rubber polymer.

So-called in this manual rubber polymer is meant that the second-order transition temperature that means soft section is below 25 ℃ by hard section and soft section polymkeric substance that constitutes.

Be not particularly limited as above-mentioned rubber polymer, can enumerate for example styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, vinylbenzene-styrenic elastomericss such as iso-butylene segmented copolymer; Thermoplastic elastomers such as low-crystalline polybutadiene, ethylene-propylene elastomeric, styrene-grafted ethylene-propylene elastomeric, thermoplastic polyester elastomer, vinyl ionomer resin etc.These rubber polymers can be used specific functional group modification such as epoxy group(ing), carboxyl, hydroxyl, amino, anhydride group, oxazolinyl.Optimization styrene class elastomerics wherein.

As above-mentioned styrenic elastomerics, if under the situation of the optical characteristics of the present invention's the 1st who does not damage manufacturing TPSNB resin film, can improve physical propertys such as modulus in tension, tension fracture elongation rate, then be not particularly limited, can enumerate the multipolymer that vinylbenzene segment and the second-order transition temperature segment below 25 ℃ for example constitutes, wherein, optimization styrene-ethylene-butene copolymer (SEBS) and styrene-ethylene-propylene copolymer etc.Styrene-ethylene-butylene copolymer of vinylbenzene composition 25～50 weight %, ethene composition 25～50 weight % can obtain to have simultaneously the blooming of high optical characteristics and physical property, and is therefore preferred especially.This is considered to extremely approaching with the resinoid specific refractory power of TPSNB, and the reduction that can efficiently give the character of rubber and spring rate is also little, does not therefore damage the cause of the resinoid characteristic of TPSNB.

When using the styrenic elastomerics as above-mentioned rubber polymer, the elastomeric number-average molecular weight of preferred above-mentioned styrenic is 50,000～1,000,000.If less than 50,000, dispersiveness in norbornene resin becomes insufficient, sometimes can't obtain the modified effect of the physical property that interpolation produced of rubber polymer, if surpass 1,000,000, melt viscosity when cooperating in norbornene resin is too high, sometimes insufficient formability can not obtain the film of homogeneous.More preferably 80,000～500,000, more preferably 100,000～400,000.

The difference of the specific refractory power of above-mentioned TPSNB resinoid and rubber polymer is preferably below 0.2.If surpass 0.2, deteriorations such as the transparency of the present invention's the 1st of manufacturing TPSNB resin film, residual phase difference are easy to generate optical skew etc. sometimes.More preferably below 0.1, more preferably below 0.05, be preferably below 0.03 especially.

In addition, when modulating above-mentioned TPSNB based resin composition by melting mixing, the ratio (η rubber/η norbornylene) of the viscosity (η rubber) of resinoid viscosity of above-mentioned TPSNB (η norbornylene) and rubber polymer is preferably near 1 under the mold temperature.Above-mentioned rubber polymer is little to be scattered in the above-mentioned TPSNB resinoid if viscosity ratio near 1, then can make.Be preferably 0.2～3.0, more preferably 0.4～2.0.When the haze value of the TPSNB resin film that makes manufacturing is below 0.5%, preferred especially η rubber/the η norbornylene is 0.5～1.8.Here said viscosity means that in actual mold temperature down cut speed be the viscosity of measuring at 24.3 o'clock.

For above-mentioned TPSNB based resin composition 100 weight parts in the above-mentioned TPSNB based resin composition, the content of above-mentioned rubber polymer is preferably 5～40 weight parts.If less than 5 weight parts, can't obtain the present invention the 1st the TPSNB resin film sufficient physical property improve effect, if surpass 40 weight parts, the optical characteristics of the TPSNB resin film of the present invention of manufacturing.Be preferably 10～30 weight parts.

Preferred above-mentioned TPSNB resin combination also contains thermoplastic resin.By containing above-mentioned thermoplastic resin, the consistency of above-mentioned sometimes TPSNB resinoid and rubber polymer improves, and the optical characteristics of the present invention's the 1st of manufacturing TPSNB resin film improves.

As above-mentioned thermoplastic resin, be not particularly limited since with the resinoid consistency excellence of TPSNB, so preferred alkenes resinoid.

The number-average molecular weight of above-mentioned thermoplastic resin is preferably 300～10,000.If less than 300 produces problem such as ooze out sometimes,, can not obtain consistency sometimes and improve effect if surpass 10,000.More preferably 500～5000, more preferably 600～2000.

Preferred above-mentioned thermoplastic resin and the resinoid refringence of above-mentioned TPSNB are below 0.2.If surpass 0.2, the transparency of the present invention's the 1st of Zhi Zaoing TPSNB resin film is poor sometimes.More preferably below 0.1.

In addition, when adopting the melting mixing method to cooperate above-mentioned thermoplastic resin in the TPSNB resin combination, as above-mentioned thermoplastic resin, preferably 20 weight % decomposition temperatures under air atmosphere are more than 230 ℃ in thermogravimetric analysis.More preferably more than 250 ℃, more preferably more than 270 ℃.

As the commercially available product in the thermoplastic resin with this character, can enumerate for example TONEX society system " Escorez ", YASUHARA CHEMICAL society system " CLEARON ", waste river chemistry society's system " ARKON " etc.

Above-mentioned TPSNB resin combination is in the scope of not damaging purpose of the present invention, can contain 2 as required, 6-di-t-butyl-4-sylvan, 2-(1-methylcyclohexyl)-4,6-dimethyl phenol, 2,2-methylene radical-two-(4-ethyl-6-tert-butyl phenol), three oxidation inhibitor such as (dinonyl phenyl phosphate ester); To tert-butyl-phenyl salicylate, 2, UV light absorber such as 2 '-dihydroxyl-4-methoxyl group benzophenone, 2-(2 '-dihydroxyl-4 '-octyloxyphenyl) benzotriazole; Paraffin, sclerosis wet goods lubricant; Stearamide propyl dimethyl-static inhibitor such as beta-hydroxyethyl ammonium nitrate etc.

The parallel rays transmitance of the present invention the 1st TPSNB resin film is more than 87%.If less than 87% is used the difficulty that becomes in purposes such as polarizer protecting film.Be preferably more than 89%.

The present invention the 1st the preferred haze value of TPSNB resin film is below 5%.If surpass 5%, when in purposes such as polarizer protecting film, using, become the reason of light leakage etc. sometimes.More preferably below 3%, more preferably below 1%, be preferably below 0.5% especially.

The preferred residual phase difference of the present invention the 1st TPSNB resin film is below the 3nm, and optical axis deviation is below ± 10 ° with respect to major axis (MD) direction.If the residual phase difference surpasses 3nm, optical axis deviation surpasses ± 10 ° with respect to long axis direction, then with the present invention the 1st TPSNB resin film during as polarizer protecting film etc., becomes the reason of light leakage etc. sometimes.Residual phase difference and optical axis deviation are preferably the smaller the better; if the residual phase difference is below the 1nm, can ignore the size of optical axis deviation, do not need to check the operation of optical axis deviation; therefore can make significantly and make the simplification of the isochronous manufacturing process of polarizer protecting film, more preferably.

So-called above-mentioned optical axis is meant the direction of the specific refractory power maximum of incident beam, is commonly referred to as the axle of slow phase axle, and so-called above-mentioned optical axis deviation is meant the deviation for the angle of the long axis direction of above-mentioned optical axis.In addition, so-called long axis direction is the flow direction of the extrusion moulding when for example adopting extrusion moulding to make film.

The present invention the 1st TPSNB resin film, the modulus in tension of measuring according to JIS K 7113 is preferably more than the 900MPa.If not enough 900MPa during as polarizer protecting film, can not suppress the contraction of polarizer with the present invention the 1st TPSNB resin film sometimes.More preferably more than the 1000MPa.Modulus in tension is preferably high more good more, and the upper limit does not have special restriction.

The present invention the 1st TPSNB resin film, the tension fracture elongation rate of measuring according to JIS K 7113 is preferably 4～40%.If less than 4%; fracture easily; therefore when the TPSNB resin film with the present invention the 1st is used as polarizer protecting film; sometimes the usability once more of polarizer is poor; if surpass 40%, carry out long duration test, when particularly heat-resisting degraded is tested; the dimensional change of polaroid increases, and is easy to generate change of optical property and peeling off from liquid crystal cells sometimes.More preferably 6～35%, more preferably more than 8%.

The present invention the 1st TPSNB resin film preferably at room temperature can batch under the situation that does not have fracture with tension force 500N/650mm.Thereby can carry out mass production, cutting down cost significantly.

The present invention the 1st TPSNB resin film, preferred light coefficient of elasticity are 2.0 * 10 ^-11Pa ^-1Below.When the TPSNB resin film with the present invention the 1st is used as polarizer protecting film, add the string stress of polarizer, the stress that the distortion when fitting produces, the various external force such as stress that the distortion when being assembled on the indicating meter produces.Especially under hot and humid environment, the string stress of polarizer is big.So-called photoelastic coefficient is meant by following formula and calculates that the expression double refraction is for the value of the variation of external force.

Photoelastic coefficient (c)=double refraction (Δ n)/stress (σ)

That is, photoelastic coefficient is more little, and the variable quantity of the degree of birefringence that external force produces is more little.If photoelastic coefficient surpasses 2.0 * 10 ^-11Pa ^-1, because the distortion that external force produces, optical characteristics changes significantly, therefore uses the difficulty that becomes in the purposes of blooming.More preferably 1.0 * 10 ^-11Pa ^-1Below.

The thickness of the present invention the 1st TPSNB resin film is not particularly limited, and when average film thickness is 100 μ m when following, preferably satisfies above-mentioned optical characteristics and physical property.For the blooming that constitutes by in the past TPSNB resinoid, be below the 100 μ m if make average film thickness, then becoming is highly brittle, and makes difficulty, and during used as polarizer protecting film, the usability once more of polaroid is poor.More preferably average film thickness is below the 70 μ m, and further preferred average film thickness is below the 50 μ m, satisfies above-mentioned optical characteristics and physical property this moment.If satisfy above-mentioned optical characteristics and physical property below the average film thickness 50 μ m, then cutting down cost significantly is worth high.Lower limit for average film thickness is not particularly limited, if but be considered as uses such as blooming and polarizer protecting film, preferred average film thickness is 25 μ m when above, more preferably average film thickness is 20 μ m when above, satisfies above-mentioned optical characteristics and physical property.

In addition, the present invention the 1st TPSNB resin film, the maximum value when preferably measuring thickness according to the method for JIS K 7130 and the difference of minimum value are below the 5 μ m.Wherein, during mensuration, for the end, promptly each part of 10% of the both sides of the full width length of the film of extruding from punch die is not measured.

What present inventors studied with keen determination found that: when there was fluctuation in the thickness of film, when especially there was fluctuation in the thickness of flow direction the during extrusion moulding of film and vertical direction (TD), the tension fracture elongation was also fluctuated widely.If the difference of the thickness of film surpasses 5 μ m, even can satisfy above-mentioned value, the industrial sometimes variation of usability once more as the tension fracture elongation of mean value.

Do not exist this to have the TPSNB resin film of optical characteristics and physical property concurrently in the past, what present inventors studied with keen determination found that: by the state of above-mentioned TPSNB resinoid and rubber polymer in the control TPSNB resin film, can take into account optical characteristics and physical property, thereby finish the present invention.

Promptly, with the present invention the 1st TPSNB resin film with dyeing such as ruthenium tetroxides after, section is into about 0.05 μ m thickness, when using its section of infiltration type electron microscope observation, in the resinoid matrix of above-mentioned TPSNB, be orientated in a certain direction and be arranged in thread or during zonal state, the TPSNB resin film can have above-mentioned optical characteristics and physical property concurrently when above-mentioned rubber polymer becomes.The mode chart of 1 example of infiltration type electron microscopic mirror image of TPSNB resin film that expression is in the present invention the 1st of this state is shown in Fig. 1.

In Fig. 1, in the matrix that TPSNB resinoid 1 constitutes, rubber polymer 2 is orientated in a certain direction and is arranged in thread or banded.Size thread or zonal rubber polymer is not particularly limited, be preferably about wide 10nm, thick tens of～hundreds of nm about, about long 0.4～5 μ m.

Arrow among Fig. 1 is represented the thickness direction of TPSNB resin film, becomes problem in the optical characteristics such as parallel rays transmitance of this direction.

When having this specific structure, the present invention the 1st TPSNB resin film can have high optical characteristics and physical property simultaneously.This is considered to because when thickness direction is seen TPSNB resin film of the present invention, in the TPSNB resinoid rubber polymer with thickness tens of～hundreds of nm about, it is the following bar-shaped or banded dispersion of visible light wavelength, therefore even when cooperating a large amount of rubber polymer that makes that physical property fully improves, also can obtain clear films.

In addition, in the present invention the 1st TPSNB resin film, more preferably, when at length observing the rubber polymer that in the matrix that constitutes by the TPSNB resinoid, becomes thread or banded orientations in a certain direction, present the structure that the resinoid layer of TPSNB enters the inboard of the thread or zonal rubber polymer of at least a portion.1 for example shown in Fig. 1 b of this structure.

In Fig. 1 b, can see the TPSNB resinoid 1 in the matrix that constitutes by TPSNB resinoid 1 in the inside of thread or zonal rubber polymer 2.This structure is commonly referred to as garlic intestines structure.When the present invention the 1st TPSNB resin film had garlic intestines structure, optical properties such as physicals, the reduction of residual phase difference further improved.

This is considered to owing to when stretching the present invention the 1st TPSNB resin film etc. applies power, at first, stress concentration is on the interface of TPSNB resinoid with this garlic intestines structure and rubber polymer, and the distortion when being used for the power of the disrumpent feelings grade of film, as the moulding of the major cause of residual phase difference obtains relaxing.

On the other hand, for example,, observe the structure of irregular agglutinative rubber polymer emersion in the matrix that the TPSNB resinoid constitutes if open the TPSNB resin film in the past of record in the flat 5-148413 communique etc. with infiltration type electron microscope observation spy.The mode chart of representing 1 example of this state is shown in Fig. 2.

In Fig. 2, in the matrix that constitutes by TPSNB resinoid 1, dispose the aggegation piece of the rubber polymer 2 of all size brokenly.

In being in the TPSNB resin film of this state,, light when having cooperated a large amount of rubber polymers, can not obtain sufficient optical characteristics because at the film scattering-in, therefore thinking.

In order to suppress the state of TPSNB resinoid and rubber polymer in the TPSNB resin film as mentioned above, manufacturing has the present invention's the 1st of excellent optical and physical property TPSNB resin film, importantly with above-mentioned TPSNB resinoid and rubber polymer and various additive thorough mixing as required, behind the modulation TPSNB based resin composition, with special temperature treatment is that the basis melt extrudes, and then the temperature condition of the film after extruding is also carried out special temperature treatment.

Promptly, when employing melt extrudes manufactured TPSNB resin film, is the resinoid second-order transition temperature of TPSNB+below 135 ℃ by making the fusion of TPSNB based resin composition up to the melt temperature of the TPSNB based resin composition of sending into punch die, and making from fusion is below 40 minutes up to the average perfectly straight time of sending into punch die, can realize the TPSNB resinoid shown in Figure 1 and the state of rubber polymer, make the present invention's the 1st who satisfies optical characteristics and physical property simultaneously TPSNB resin film.

The TPSNB based resin composition that contains rubber polymer, for example also on the books in No. 2940014 communiques of special permission.But, still do not have so far to use and contain the TPSNB based resin composition of rubber polymer, even consider the measure that alleviates as the integral defectives such as flake of the performance of blooming that makes on the film, make the report of the example of blooming.In order to alleviate the flake on the film, it is indispensable using resin filter etc. to filter in extruding operation, in order to satisfy the desired performance of blooming, needs to use the high filtering precision of the resin filter of the following filtering accuracy of 10 μ m especially.During the tree filter of the filtering accuracy below using 10 μ m, have to make the resin filter to increase, have the tendency of the average retention time growth of resin because the pressure-losses is high.In addition, the rising of the pressure-losses of considering mesh that continuous use produces to block and producing is for the reduction of the film rerum natura that degraded produced that do not cause resin, in order to make the resin lowering viscousity, the pressure-losses at filter place is reduced, and moulding has at high temperature become general knowledge.But, present inventors find: if adopt the TPSNB based resin composition that this method in the past will contain rubber polymer to be shaped to film like, the rubber polymer that is contained causes aggegation, can't obtain parallel rays transmitance height, the blooming that haze value is little.

If melt temperature surpasses the temperature of the resinoid second-order transition temperature of TPSNB+135 ℃, perhaps average retention time was above 40 minutes, the aggegation of rubber polymer produces, can't realize the TPSNB resinoid shown in Figure 1 and the state of rubber polymer, the parallel rays transmitance of the TPSNB resin film of manufacturing and mist degree worsen.Preferred melt temperature is the resinoid second-order transition temperature of TPSNB+below 130 ℃.Preferred average retention time is below 35 minutes, and preferred average retention time is below 30 minutes.The manufacture method of this TPSNB resin film also is one of the present invention.

In addition, the TPSNB based resin composition that contains rubber polymer is compared the tendency that exists melt viscosity to reduce with TPSNB resinoid monomer.Therefore, when using the manufacture method manufacturing TPSNB resin film of TPSNB resin film of the present invention, moulding at low temperatures suppresses the resinoid gelation of TPSNB, for a long time continuous production.This also can be described as one of effect of using rubber polymer.About the resinoid gelation of TPSNB, present inventors find: when making the TPSNB resinoid keep temperature certain under nitrogen atmosphere, when using differential scanning calorimetry (DSC) to measure second-order transition temperature in per 1 hour, when making second-order transition temperature rise time of 1 ℃ when reaching 40 hours temperature and being melt temperature, the resinoid gelation of TPSNB can be suppressed especially, the flake of the film of manufacturing can be reduced.By under this temperature condition, carrying out moulding, continuous production for a long time.

Method as melt extruding is not particularly limited, and can use known method in the past, can enumerate for example use single screw rod, twin-screw mixer after, melt extrude with T type punch die and to be film like, it is drawn to cooling roller, carry out the method for cooling curing etc.

Method as the above-mentioned TPSNB based resin composition of modulation, be not particularly limited, can enumerate and for example use single screw mixing machine, mixing machine, twin-screw mixer machine etc. under the temperature that resinoid second-order transition temperature is high 50～150 ℃ than TPSNB, to carry out the method for melting mixing; Under super critical condition, carry out mixing method; After being dissolved in the appropriate solvent, the method that employing freezing method, casting method or direct drying method are removed solvent etc.

The modulation of TPSNB based resin composition and film forming can carry out in a series of operation, also the TPSNB based resin composition once can be modulated to granular after, use this particle to carry out film forming.

In the manufacture method of TPSNB resin film of the present invention, preferably export to the distance of the point of contact of cooling roller from punch die, promptly the space is below the 100mm.If the space is below the 100mm, in operation, be not subject to externalities, can obtain the film of thickness, optical property homogeneous.

In addition, in the manufacture method of TPSNB resin film of the present invention, preferably the temperature of the TPSNB based resin composition of extruding from punch die before contacting with cooling roller is the resinoid second-order transition temperature of TPSNB+more than 50 ℃.By being more than second-order transition temperature+50 ℃, the stress that produces when being shaped to the TPSNB resin film by the TPSNB based resin composition significantly reduces, and can suppress the generation of residual phase difference.This is that the temperature of resin becomes high temperature, does not produce stress when then being out of shape because under the situation of the such amorphism thermoplastic resin of TPSNB resinoid.More preferably more than second-order transition temperature+80 ℃.

In addition, preferably making the fluctuation that contacts the temperature of preceding TPSNB based resin composition with cooling roller is 10 ℃ of less thaies.Even when as mentioned above the temperature of TPSNB based resin composition being adjusted into more than second-order transition temperature+50 ℃, if temperature produces fluctuation, stress for the resin distortion produces fluctuation, therefore the difference because of resin might make the fluctuation of residual phase difference, and also possible stress concentration produces the deviation of optical axis in a part.

In addition, in the manufacture method of TPSNB resin film of the present invention, the temperature of preferred TPSNB based resin composition after just having extruded from punch die is the resinoid second-order transition temperature of TPSNB+more than 100 ℃.If 100 ℃ of less thaies, the stress that produces during moulding might enlarge markedly, and it is poor to be easy to generate residual phase.

As the method that the temperature of the TPSNB based resin composition extruded from punch die is like this controlled, be not particularly limited, can enumerate the temperature control equipment that for example possesses pid control function, the temperature of control punch die, the method for temperature of polymkeric substance pipe arrangement (adapter) by use.In this case, the temperature of the temperature of punch die, polymkeric substance pipe arrangement (adapter) is the temperature that resin does not produce extent of thermal degradation.In addition, in the space, also considered the use heater heats, or used insulation cover etc., the method that film is incubated.In this case, compare with changing the punch die method of temperature, can carry out temperature control accurately, temperature fluctuation reduces, and is effective especially for requiring to carry out accurately temperature controlled situation.In addition, because punch die excessive temperature ground is risen, therefore also has the advantage that suppresses the resin degraded.

In addition, when making the TPSNB based resin composition contact cooling roller that melt extrudes, preferably in the downstream side of point of contact, for cooling roller extruding TPSNB based resin composition.The temperature variation of the TPSNB based resin composition homogeneous that becomes can prevent the generation of optical axis deviation like this, and the gradient that obtains thickness is stable, the film of homogeneous thickness.

Method as the TPSNB based resin composition being expressed to cooling roller is not particularly limited, and can enumerate for example methods such as air knife, wind box, static pinning, touch roll.At this moment, the more preferably temperature of width, pressure homogeneous.

The surfaceness Ry of above-mentioned cooling roller is preferably below the 0.5 μ m.If surpass 0.5 μ m, can't keep the smoothness of TPSNB based resin composition, the transparency of the TPSNB resin film of Zhi Zaoing is poor sometimes.More preferably below the 0.3 μ m.Above-mentioned surfaceness can be measured for the method for benchmark according to JIS B 0601.In addition, as the material of above-mentioned cooling roller, there is no particular restriction, can enumerate for example carbon steel, stainless steel etc.

In the manufacture method of TPSNB resin film of the present invention, the gap that is preferably mounted at the punch die outlet of employed forcing machine preestablishes according to the flow path designs of punch die.The fluctuation of permission and above-mentioned thickness is with the error of degree.In addition, when having a plurality of gaps adjusting pin at punch die, the thickness adjustment in the time of in fact can be according to extrusion film.

The present invention the 1st TPSNB resin film can have high optical characteristics and physical property concurrently as mentioned above, therefore is preferably used as blooming.

The blooming that the present invention the 1st TPSNB resin film constitutes also is one of the present invention.

The present invention the 1st TPSNB resin film also is preferably used as polarizer protecting film.The polarizer protecting film that is made of the present invention the 1st TPSNB resin film also is one of the present invention.

Polarizer protecting film of the present invention can carry out various surface treatments according to the purposes of the liquid-crystal display that uses.As above-mentioned surface treatment, be not particularly limited, can enumerate for example transparent hard coat processing, AG (anti-mirroring) processing, AR (antireflection) processing etc.

Polarizer protecting film of the present invention is a purpose with the stickiness that improves with polarizer in the scope of not damaging optical characteristics, can implement Corona discharge Treatment so that the contact angle of surface and water reaches about 40～50 degree.

The present invention the 1st TPSNB resin film is given orientation by unidirectional or two-way stretch, the phase difference film of the deviation of compensation light when also being preferably used as by liquid crystal material.The phase difference film that is made of the present invention the 1st TPSNB resin film also is one of the present invention.In addition, phase difference film of the present invention directly is laminated on the single face at least of polarizer and the polaroid that forms also is one of the present invention.

Be not particularly limited as carrying out above-mentioned tensile temperature, be preferably the resinoid second-order transition temperature of above-mentioned TPSNB～resinoid second-order transition temperature of above-mentioned TPSNB+20 ℃.If outside this scope, film is disrumpent feelings sometimes at low temperature side, can not obtain required phase difference value sometimes at high temperature side.The resinoid second-order transition temperature of the more preferably above-mentioned TPSNB+resinoid second-order transition temperature of 1 ℃～above-mentioned TPSNB+10 ℃.

Stretching ratio when carrying out above-mentioned stretching is not particularly limited, when along film melt extrude direction when stretching, be preferably 1.05～5.0 times.If 1.05 times of less thaies, deflection is very few, can't obtain sufficient phase differential sometimes, if surpass 5.0 times, film is disrumpent feelings sometimes.Preferred 1.1～2.5 times.In addition, when along with film melt extrude the vertical direction of direction when stretching, be preferably 1.2～3.0 times, more preferably 1.5～2.5.

The present invention the 2nd relates to the polaroid that the polarizer protecting film that is made of the norbornene resin composition and polarizer constitute; the parallel rays transmitance of this polaroid is more than 40%; under condition, do not have when peeling off under draw speed 300mm/min, the tension force 2.5～3N/25mm disrumpent feelings according to 180 ° of stripping tests of JIS Z 1528.

Be not particularly limited as above-mentioned polarizer, can use known in the past polarizer, for example, can use iodine or dichroic dye to be adsorbed on the polyvinyl alcohol resin of stretch orientation and the polarizer that forms etc.

The present invention the 2nd polaroid does not have when peeling off under draw speed 300mm/min, the tension force 2.5～3N/25mm disrumpent feelings under the condition according to 180 ° of stripping tests of JIS Z 1528.

Usually, polaroid and liquid crystal cells are also peeled off because of the stress that the polarizer of formations such as polyvinyl alcohol wants thermal contraction to produce, and require to carry out bonding with the intensity that can suppress all dimensional change degree of polaroid.Necessary for this reason bonding force is considered in 180 ° of stripping tests according to JIS Z 1528, and surveying periodic stripping strength with draw speed 300mm/min is about 2.5～3N/25mm.Therefore, have under the condition according to 180 ° of stripping tests of JIS Z 1528, do not have the present invention's the 2nd of disrumpent feelings character polaroid when peeling off with draw speed 300mm/min, tension force 2.5～3N/25mm, it is the usability excellence once more.

The parallel rays transmitance of the present invention the 2nd polaroid is more than 40%.If less than 40%, produce following rough sledding when being used as liquid crystal with polaroid: the lightness deficiency of the image of demonstration, image is ugly.

The present invention the 2nd polaroid carries out 24 hours size changing rates before and after the heating and is preferably below 20% under 90 ℃.If surpass 2%, the stress that produces when not making polaroid and liquid crystal cells because of dimensional change is peeled off, must be to surpass the high strength bonding of 3N/25mm, and usability is poor once more sometimes.

Method as the polaroid of making the present invention the 2nd is not particularly limited, and can enumerate caking agents such as for example using polyurethanes, polyester, polyacrylic; The method that known in the past caking agent such as the caking agent of acrylic acid or the like, silicon class, rubber-like is bonding with the polarizer protecting film of the present invention of above-mentioned polarizer and the present invention's the 1st TPSNB resin film formation etc.When bonding, can not reduce at the polarization property of polarizer under the condition of appropriateness of degree and add heat setting.

The present invention the 2nd polaroid shows high optical characteristics, also has high usability once more.

Embodiment

Below enumerate embodiment the present invention is described in more detail, but the present invention has more than and is limited to these embodiment.

(embodiment 1)

(1) the TPSNB resin film is made

With 90: 10 weight ratios TPSNB resinoid (JSR society system, ARTON G6810: 164 ℃ of second-order transition temperatures, specific refractory power 1.52) and styrenic elastomerics (society of Asahi Chemical Industry system, TuftecH1041: specific refractory power 1.51, styrene content 32%, ethylene content 43%) are supplied to twin screw and melt extrude machine, 286 ℃ of following melting mixing and carry out granulation, descended predrying 3 hours modulation TPSNB based resin composition at 110 ℃.

Use the TPSNB based resin composition of making,, under the temperature condition of table 1 record, carry out extrusion moulding, obtain the blooming of mean thickness 40 μ m by following forcing machine, T type punch die and resin filter.

Forcing machine: the single screw extrusion machine that has T type punch die of diameter 90mm, L/D=28

T type punch die: the clothes hanger type of wide 1500mm, resin flow road surfaces are implemented the H-Cr plating

Resin filter: leaf dish-type strainer (Japanese smart line society system, filter precision 10 μ m)

In addition, use surface mounting the Elastic Contact roller of metal sleeve as the contact stabilizing deyice.The Elastic Contact roller of this moment and the temperature of cooling roller are set at 70 ℃.In addition, the surfaceness of Elastic Contact roller and cooling roller is expressed as 0.2 μ m with Ry.Temperature before contacting with cooling roller is using non-contact thermometer to measure under the isolating state from the cooling roller on the Elastic Contact roller.

For the TPSNB resinoid that uses, under 99.9% nitrogen wash, after remaining on 286 ℃, when the proportional flow of dividing with 60mL/ on the limit with DSC (SEIKO INSTRUMENTS society system, DSC6200R) is crossed the nitrogen limit and is measured second-order transition temperature, obtain up to the time of 1 ℃ of second-order transition temperature rising, it is 120 hours.

(2) making of polaroid

With the water of room temperature with polyvinyl alcohol (polymerization degree 3800, the saponification deg: (thickness: 75 μ m) after the washing of non-stretched film 99.5 moles of %), on the vertical single ax direction, carry out 6 times of stretchings, under keeping this stretched state, impregnated in the aqueous solution that contains iodine 0.5 weight % and potassiumiodide 5 weight %, in 50 ℃ the aqueous solution that contains boric acid 10 weight % and potassiumiodide 10 weight %, carry out 5 minutes crosslinking Treatment then, make polarizer.

Use the TPSNB resin film of making as polarizer protecting film.

At first, with the face of the stacked side of polarizer of film surface on implement Corona discharge Treatment.Polarizer protecting film surface after the Corona discharge Treatment is 42～44 degree with the contact angle of water.Then; water with the mixture diluted of A agent/B agent=10/3 (weight ratio) of 2 liquid mixed type watersoluble polyurethane class caking agents (Japan morton society system, EL-436A/B) so that solids component reaches 10 weight %; the modulation adhesive solution; use Mayer bar#8 on the Corona discharge Treatment face of polaroid protective film, to be coated with; it is fitted on the two sides of polarizer, obtain duplexer.

The duplexer of making was kept 72 hours in 45 ℃ thermostatic bath, carry out drying, health, make polaroid.

(embodiment 2)

With 85: 15 weight ratios the TPSNB resinoid (JSR society system, ARTONG6810) that uses among the embodiment 1 and styrenic elastomerics (KARTON polymkeric substance society system, G1652: specific refractory power 1.52, styrene content 28%, ethylene content 45%) are supplied to twin screw and melt extrude machine, 286 ℃ of following melting mixing, sending into temperature regulation with 30 minutes residence time is 286 ℃ T type punch die.Except adopting the condition shown in the table 1, make the TPSNB resin film of thickness 30 μ m similarly to Example 1.Use the TPSNB resin film of making as polaroid protective film, adopt method similarly to Example 1 to make polaroid.

(embodiment 3)

With 90: 10 weight ratios the TPSNB resinoid (JSR society system, ARTONG6810) that uses among the embodiment 1 and styrenic elastomerics (society of Asahi Chemical Industry system, Tuftec1041) are supplied to twin screw and melt extrude machine, 293 ℃ of following melting mixing, sending into temperature regulation with 30 minutes residence time is 293 ℃ T type punch die.Except adopting the condition shown in the table 1, make the TPSNB resin film of thickness 30 μ m similarly to Example 1.Use the TPSNB resin film of making as polaroid protective film, adopt method similarly to Example 1 to make polaroid.

For the TPSNB resinoid that uses, under 99.9% nitrogen wash, after remaining on 293 ℃, when the proportional flow of dividing with 60mL/ on the limit with DSC (SEIKO INSTRUMENTS society system, DSC6200R) is crossed the nitrogen limit and is measured second-order transition temperature, obtain up to the time of 1 ℃ of second-order transition temperature rising, it is 40 hours.

(embodiment 4)

With 80.5: 15: 4.5 weight ratios TPSNB resinoid (JSR society system, ARTON G6810), styrenic elastomerics (KARTON polymkeric substance society system, KARTONRP6936: specific refractory power 1.51, styrene content 40%) and the thermoplastic resin (TONEX society system, Escorez235E) that uses among the embodiment 1 supplied to twin screw and melt extrude machine, 286 ℃ of following melting mixing, predrying 3 hours of the particle that under 110 ℃ granulation is obtained obtains the TPSNB based resin composition.

Use the TPSNB based resin composition of making, except adopting the condition shown in the table 1, make the TPSNB resin film of thickness 40 μ m similarly to Example 1.Use the TPSNB resin film of making as polaroid protective film, adopt method similarly to Example 1 to make polaroid.

(embodiment 5)

With 85: 15 weight ratios the TPSNB resinoid (JSR society system, ARTONG6810) that uses among the embodiment 1 and styrenic elastomerics (KARTON polymkeric substance society system, KARTONRP6936) are supplied to twin screw and melt extrude machine, 286 ℃ of following melting mixing, predrying 3 hours of the particle that under 110 ℃ granulation is obtained obtains the TPSNB based resin composition.

Use the TPSNB based resin composition of making, except adopting the condition shown in the table 1, make the TPSNB resin film of thickness 40 μ m similarly to Example 1.Use the TPSNB resin film of making as polaroid protective film, adopt method similarly to Example 1 to make polaroid.

(embodiment 6)

With 89: 10: 1 weight ratios TPSNB resinoid (JSR society system, ARTON G6810), styrenic elastomerics (KARTON polymkeric substance society system, KARTONRP6936: specific refractory power 1.51, styrene content 40%) and the thermoplastic resin (TONEX society system, Escorez235E) that uses among the embodiment 1 supplied to twin screw and melt extrude machine, 286 ℃ of following melting mixing, predrying 3 hours of the particle that under 110 ℃ granulation is obtained obtains the TPSNB based resin composition.

Use the TPSNB based resin composition of making, except adopting the condition shown in the table 1, make the TPSNB resin film of thickness 40 μ m similarly to Example 1.Use the TPSNB resin film of making as polaroid protective film, adopt method similarly to Example 1 to make polaroid.

(comparative example 1)

Only the TPSNB resinoid (JSR society system, ARTON G6810) that uses among the embodiment 1 is supplied to single screw rod and melt extrude machine, except adopting the condition shown in the table 1, make the TPSNB resin film of thickness 30 μ m similarly to Example 1.Use the TPSNB resin film of making as polaroid protective film, adopt method similarly to Example 1 to make polaroid.

(comparative example 2)

Average retention time in making forcing machine is 50 minutes, makes TPSNB resin film and polaroid similarly to Example 5.

(comparative example 3)

Except making extrusion temperature is 310 ℃, makes TPSNB resin film and polaroid similarly to Example 5.

For the TPSNB resinoid that uses, under 99.9% nitrogen wash, after remaining on 310 ℃, when the proportional flow of dividing with 60mL/ on the limit with DSC (SEIKO INSTRUMENTS society system, DSC6200R) is crossed the nitrogen limit and is measured second-order transition temperature, obtain up to the time of 1 ℃ of second-order transition temperature rising, it is 12 hours.

(comparative example 4)

Modulation is dissolved in the solution in the toluene with 90: 10 weight ratio with TPSNB resinoid (JSR society system, ARTON G6810) and the styrenic elastomerics (KARTON polymkeric substance society system, G1652) that uses among the embodiment 1, uses this solution to adopt casting method to make the TPSNB resin film of thickness 40 μ m.

The TPSNB resinoid of the TPSNB resin film of making and styrenic elastomerics produce and are separated, and are heterogeneity, opaque film.

Use the TPSNB resin film of making as polaroid protective film, adopt method similarly to Example 1 to make polaroid.

For the TPSNB resin film of making in embodiment 1～6 and the comparative example 1～4, adopt that following method measures that modulus in tension, tension fracture elongation, total light transmittance, parallel rays transmitance, haze value, residual phase are poor, optical axis deviation, photoelastic coefficient, the fluctuation of film thickness, the generation of flake and batching property.In addition, for the TPSNB resin film that embodiment 1 makes, adopt following method to use TEM to observe, evaluation has or not garlic intestines structure.

In addition, for the polaroid of making in embodiment 1～6 and the comparative example 1～4, adopt following method to measure the parallel rays transmitance, in addition, breaking property and weather resistance when peeling off are estimated.

The results are shown in table 2, table 3 and Fig. 3.

(1) mensuration of the modulus in tension of TPSNB resin film and tension fracture elongation

According to JIS K 7113, use TENSILON (ORIENTEC society system), measure under the following conditions.

Spacing jig is from 150mm

Film is wide: 20mm

Draw speed: 20mm/ branch

(2) mensuration of the total light transmittance of TPSNB resin film, parallel rays transmitance and haze value

Use haze meter (Tokyo electricity look society system, TC-HIIIDKP), measure according to JIS K 7105.

(3) mensuration of poor, the optical axis deviation of the residual phase of TPSNB resin film

Use automatic double refraction meter (prince's instrumentation machine society system, KOBRA-21ADH), under mensuration wavelength 590nm, measure.

(4) mensuration of the photoelastic coefficient of TPSNB resin film

Film is cut out wide 10mm * long 100mm, apply on the long side direction 0,500,1000 and the state of the load of 1500g under, use prince's instrumentation machine society system, KOBRA-21ADH, measure phase differential measuring under the wavelength 550nm.The slope of the near linear when drawing phase differential to the figure of load is obtained photoelastic coefficient.

(5) mensuration of the fluctuation of the thickness of TPSNB resin film

Employing is obtained the poor of maximum value at this moment and minimum value according to the thickness of the method mensuration film of JIS K 7130.Use the Millitron1240 of seikoEM society system in the mensuration.

(6) evaluation of flake generation

The number of the square above flake of 100 μ m in the film that visual observation is made is measured from manufacturing and is begun to surpass 10/m to the generation number of flake ²Time.

(7) evaluation of the batching property of TPSNB resin film

On-line velocity 5,10 and 30m/ branch, coiling tension 500N/650mm, the volume core: under the condition that the FRP system is 6 inches, film is batched test, estimating film has non-cracking.

(8) adopt of the observation of infiltration type electron microscope to the TPSNB resin film

With ruthenium tetroxide etc. the TPSNB resin film is dyeed, use then on the flow direction (MD) and width (TD) of slicing machine when extrusion moulding, be cut into the thick thin slice of about 0.05 μ m, use infiltration type electron microscope (NEC society system, JEM-1200EX II) that two directions cross section is separately observed, take pictures.In addition, be that basic evaluation has or not garlic intestines structure with this photograph.

(9) mensuration of the parallel rays transmitance of polaroid

Use haze meter (Tokyo electricity look society system, TC-HIIIDKP), measure according to JIS K 7105.

(10) evaluation of the breaking property during the peeling off of polaroid

The adjustment of＜tackiness agent and non-support adhesive tape 〉

In the presence of benzoyl peroxide 0.3 weight part, as solvent butyl acrylate 94.8 weight parts, vinylformic acid 5 weight parts and 2-hydroxyethyl methacrylate 0.2 weight part are carried out copolymerization with ethyl acetate, obtain the ethyl acetate solution of the acrylic polymers of weight-average molecular weight (Mw) 1,200,000, molecular weight distribution 3.9.

Adding toluene in the ethyl acetate solution of the acrylic polymers of making dilutes, become the toluene solution of 13 weight % of acrylic polymers, add isocyanate crosslinking (Japanese polyurethane society system, CORONATE L) 2 weight parts and stir modulating adhesive.

With the adhesive coated made on mold release film, in order not make its foaming with 60 ℃, 5 minutes, 120 ℃, 5 minutes 2 stages are carried out drying, and then will light exfoliated mold release film be laminated to and fix on the tackiness agent face, make the non-support adhesive tape that dried thickness (mean value) is 25 μ m.

The making of＜test film 〉

The mold release film of gently peeling off side of non-support adhesive tape is peeled off, be laminated on the single face of polaroid, make polaroid adhesion sheet.The polaroid adhesion sheet of making is cut into the short palisade of 25mm * 150mm so that the angle of polarizer absorption axes constitutes the angle of 0 degree and 90 degree with respect to long limit.Then, the mold release film of non-support adhesive tape is peeled off, used the roller of pressing of heavy 2kg to fit on the non-alkali glass of thick 1.1mm.Under 50 ℃, the condition of 5 air pressure, carry out 20 minutes autoclaves again and handle, become test film.

＜stripping test 〉

Angle for the polarizer absorption axes of making is that the test film of 0 degree and the angle of polarizer absorption axes are the test film of the angles of 90 degree with respect to the length limit with respect to the length limit, TENSILON (ORIENTEC society system) is used in visual observation, under condition according to 180 ° of stripping tests of JIS Z 1528, the state of the polaroid when peeling off with draw speed 300mm/min is estimated according to following benchmark.The peeling force of this moment is about 3N/25mm.

Zero: not fracture, do not peel off fully from sheet glass

*: produce fracture in peeling off the way, a part remains on the sheet glass

(11) Evaluation of Durability of polaroid

The modulation of＜tackiness agent and non-support adhesive tape 〉

Same when the breaking property when peeling off with polaroid is estimated, make tackiness agent and non-support adhesive tape.

The making of＜test film 〉

The mold release film of gently peeling off side of non-support adhesive tape is peeled off, be laminated on the single face of polaroid of manufacturing, make polaroid adhesion sheet.Angle with the polarizer absorption axes is the size that 0 angle of spending is cut into the polaroid adhesion sheet of making 200mm * 300mm with respect to long limit.Then, the mold release film of non-support adhesive tape is peeled off,, used and pressing roller to fit on the non-alkali glass of thick 1.1mm with the pressure of 19.6N/25mm.

Preserved 3 days in 100 ℃ baking oven fitting to polaroid on glass, placed for 1 week in the thermostatic constant wet chamber of 25 ℃ of temperature, humidity 50%RH, the surface of visual observation polaroid is estimated according to following benchmark then.

Zero: do not find cracking fully, the transparency is excellent

△: find cracking, slightly gonorrhoea

*: the transparency is excellent, but finds cracking

* *: found significantly cracking, produces gonorrhoea

Table 1

	Extrusion condition
						Extrusion temperature (℃)	Residence time (branch)	Resin temperature after just having extruded (℃)	Space (mm)	Resin temperature before just will having contacted with cooling roller (℃)
	Embodiment 1	286	30	286	????90						215
Embodiment 2						286	30	286	????90	215
	Embodiment 3	293	30	293	????90						215
Embodiment 4						286	30	286	????70	230
	Embodiment 5	286	30	286	????70						230
Embodiment 6						286	30	286	????50	260
	Comparative example 1	310	50	310	????90						235
Comparative example 2						286	50	286	????70	230
	Comparative example 3	310	30	310	????70						240
Comparative example 4						-	-	-	????-	-

Table 2

	The evaluation of thermoplasticity saturated norbornene resin film
														Modulus in tension (MPa)	Tension fracture elongation rate (%)	Parallel rays transmitance (%)	Haze value (%)	Residual phase poor (nm)	Optical axis deviation (°)	Photoelastic coefficient (* 10 -11Pa -1)	Batching property (non-cracking is arranged)			Thickness fluctuation (μ m)	The generation of flake (hour)	Have or not garlic intestines structure
	The 5m/ branch	The 10m/ branch	The 30m/ branch
				Embodiment 1	1690	12	91	0.9	3.80	????±8	????0.47	Do not have	Do not have								Do not have	5	??110				Have
Embodiment 2	1560	25	91											1.0	3.70	????±7	????0.49	Do not have	Do not have	Do not have				8	??110	Have
				Embodiment 3	1710	12	92	0.7	3.20	????±8	????0.48	Do not have	Do not have								Do not have	7	??43				Have
Embodiment 4	2030	14	91											0.3	2.53	????±8	????0.45	Do not have	Do not have	Do not have				4	??110	Have
				Embodiment 5	2040	14	92	0.3	2.60	????±8	????0.45	Do not have	Do not have								Do not have	5	??110				Have
Embodiment 6	2060	12	91											0.2	0.80	????±8	????0.43	Do not have	Do not have	Do not have				4	??110	Have
				Comparative example 1	2100	2	92	0.1＞	8.90	????±5	????0.40	Have	Have								Have	5	??11				Do not have
Comparative example 2	1660	10	80											2.9	3.80	????±8	????0.47	Do not have	Do not have	Do not have				8	??95	Do not have
				Comparative example 3	1650	10	81	3.5	0.80	????±20	????0.47	Do not have	Do not have								Do not have	8	??12				Do not have
Comparative example 4	1500	8	70											15.2	-	????-	????-	??-	??-	??-				5	??-	Do not have

Table 3

	The evaluation of polaroid
					Parallel rays transmitance (%)	Endurance test	Breaking property when peeling off
	0 degree test film	90 degree test films
			Embodiment 1	42			??○	??○	??○
Embodiment 2	41	??○			??○	??○
			Embodiment 3	42			??○	??○	??○
Embodiment 4	42	??○			??○	??○
			Embodiment 5	42			??○	??○	??○
Embodiment 6	42	??○			??○	??○
			Comparative example 1	42			??×	??×	??×
Comparative example 2	38	??△			??○	??○
			Comparative example 3	38			??△	??○	??○
Comparative example 4	35	??××			??×	??×

(embodiment 9)

Use the TPSNB resin film of making among the embodiment 1 to make phase difference film.Promptly, nip rolls is arranged on the outer two ends of stove of the process furnace that longitudinally is divided into preheating zone, drawing zone, cooling zone 3 parts, certain speed with 5.0m/min rolls out continuously from the inlet side nip rolls, stretches with the stretching ratio that reaches 150% with the speed of the 7.5m/min nip rolls with outlet side simultaneously.Temperature is set at 153 ℃ of preheating zones, 166 ℃ of drawing zones, 120 ℃ of cooling zones, obtains the uniaxiality phase difference film.

For the phase difference film of making, use automatic double refraction meter (prince's instrumentation society system, KOBRA-21ADH) to measure the phase differential that the 589nm wavelength is gone into the light time, its result is 160nm.

According to the present invention, can provide the manufacture method of the thermoplasticity saturated norbornene resin film, blooming, polarizer protecting film, phase difference film, polaroid and the thermoplasticity saturated norbornene resin film that have high physical property and optical characteristics concurrently.

Need to prove that " above, following " in this specification sheets includes end points.

Claims (20)

1. thermoplasticity saturated norbornene resin film, it is characterized in that: use contains the thermoplasticity saturated norbornene based resin composition of thermoplasticity saturated norbornene resinoid 100 weight parts and rubber polymer 5～40 weight parts and forms, and the parallel rays transmitance is more than 87%.

2. thermoplasticity saturated norbornene resin film according to claim 1 is characterized in that: the difference of the specific refractory power of thermoplasticity saturated norbornene resinoid and rubber polymer is below 0.2.

3. thermoplasticity saturated norbornene resin film according to claim 1 and 2 is characterized in that: modulus in tension is more than the 900MPa, and tension fracture elongation rate is 4～40%.

4. according to claim 1,2 or 3 described thermoplasticity saturated norbornene resin films, it is characterized in that: the residual phase difference is below the 3nm, and optical axis deviation is below ± 10 ° with respect to long axis direction.

5. according to claim 1,2 or 3 described thermoplasticity saturated norbornene resin films, it is characterized in that: the residual phase difference is below the 1nm.

6. according to claim 1,2,3,4 or 5 described thermoplasticity saturated norbornene resin films, it is characterized in that: the maximum value when employing is measured thickness according to the method for JIS K 7130 and the difference of minimum value are below the 5 μ m.

7. according to claim 1,2,3,4,5 or 6 described thermoplasticity saturated norbornene resin films, it is characterized in that: can under the situation that does not make its fracture, batch with tension force 500N/650mm.

8. according to claim 1,2,3,4,5,6 or 7 described thermoplasticity saturated norbornene resin films, it is characterized in that: rubber polymer is the styrenic elastomerics.

9. thermoplasticity saturated norbornene resin film according to claim 8 is characterized in that: the styrenic elastomerics is styrene-ethylene-butylene copolymer of vinylbenzene composition 25～50 weight %, ethene composition 25～50 weight %.

10. according to claim 1,2,3,4,5,6,7,8 or 9 described thermoplasticity saturated norbornene resin films, it is characterized in that: thermoplasticity saturated norbornene resin combination also contains the thermoplastic resin of number-average molecular weight 300～10,000.

11. according to claim 1,2,3,4,5,6,7,8,9 or 10 described thermoplasticity saturated norbornene resin films, it is characterized in that: photoelastic coefficient is 2.0 * 10 ^-11Pa ^-1Below.

12. a blooming is characterized in that: constitute by claim 1,2,3,4,5,6,7,8,9,10 or 11 described thermoplasticity saturated norbornene resin films.

13. a polarizer protecting film is characterized in that: constitute by claim 1,2,3,4,5,6,7,8,9,10 or 11 described thermoplasticity saturated norbornene resin films.

14. a phase difference film is characterized in that: constitute by claim 1,2,3,4,5,6,7,8,9,10 or 11 described thermoplasticity saturated norbornene resin films.

15. polaroid; it is characterized in that: the polarizer protecting film and the polarizer that are made of the norbornene resin composition constitute; the parallel rays transmitance is more than 40%; under condition, with draw speed 300mm/min, not fracture when tension force 2.5～3N/25mm peels off according to 180 ° of stripping tests of JIS Z 1528.

16. polaroid according to claim 15 is characterized in that: carrying out 90 ℃, the 24 hours size changing rates before and after the heating is below 2%.

17. a polaroid is characterized in that: the described phase difference film of direct stacked claim 14 on the single face at least of polarizer and forming.

18. the manufacture method of a thermoplasticity saturated norbornene resin film is characterized in that: make claim 1,2,3,4,5,6,7,8,9,10 or 11 described thermoplasticity saturated norbornene resin films by extrusion by melting,

With the melt temperature of thermoplasticity saturated norbornene based resin composition fusion up to the thermoplasticity saturated norbornene based resin composition of sending into punch die, be the resinoid second-order transition temperature of thermoplasticity saturated norbornene+below 135 ℃, and will be below 40 minutes to the average retention time of sending into punch die after the fusion of thermoplasticity saturated norbornene based resin composition.

19. the manufacture method of thermoplasticity saturated norbornene resin film according to claim 18, it is characterized in that: the temperature before the contacting with cooling roller of the thermoplasticity saturated norbornene based resin composition of extruding from punch die is the resinoid second-order transition temperature of thermoplasticity saturated norbornene+more than 50 ℃.

20. the manufacture method of thermoplasticity saturated norbornene resin film according to claim 18, it is characterized in that: the temperature before the contacting with cooling roller of the thermoplasticity saturated norbornene based resin composition of extruding from punch die is the resinoid second-order transition temperature of thermoplasticity saturated norbornene+more than 80 ℃.

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